Carbohydrates

BIOCHEMISTRY-AN OVERVIEW

 Biochemistry is the study of the chemical substances found in living organisms and the
chemical interactions of these substances with each other.
 It is also a field in which new discoveries are made almost daily about how cells
manufacture the molecules needed for life and how chemical reactions by which life is
maintained occur.
 A biochemical substance is a chemical substance found within a living organisms.
 Two Groups:
 Bioinorganic Substances: Do not contain carbon; Water (70%),
Inorganic salts (5%) /two-thirds of the mass
 Bioorganic Substances: Contain carbon; Proteins (15%), Lipids (8%),
Carbohydrates (2%), Nucleic acids (2%) /one-fourth of body mass
These substances do not have life of themselves until it is gathered together in
a cell.
More than half of all organic carbon atoms are found in the carbohydrate
materials of plants.
Carbohydrates in the form of cotton and linen are used as clothing.
Carbohydrates in the form of wood are used for shelter and heating and in
making paper.

Occurence and Functions of Carbohydrates

 Carbohydrates are the most abundant class of bioorganic molecules on planet earth
although it is relatively low in the human body.
 75% by mass of dry plant materials are constituted by carbohydrates.
 Green (chlorophyll-containing) plants produce carbohydrates via photosynthesis.
 Carbon dioxide from the air and water from the soil are the reactants, and
sunlight absorbed by chlorophyll is the energy source.

 Two main uses of plants for the carbohydrates they produced:

 Cellulose: Carbohydrates serve as structural elements.
 Starch: Provide energy reserves for the plants.
 Dietary intake of plant materials is the major carbohydrate source for humans and
animals.
 Average human diet is two-thirds carbohydrate by mass.
 Functions of the Carbohydrates:
 Oxidation provides energy.
 Storage in the form of glycogen, provides a short-term energy reserve.
 Supply carbon atoms for the synthesis of other biochemical substances.
 Form part of the structural framework of DNA and RNA molecules.
 Linked to lipids are structural components of cell membranes.
 Linked to proteins function in a variety of cell-cell and cell-molecule recognition
processes.

Classification of Carbohydrates

 General formula of CnH2nOn

 A carbohydrates is a polyhydroxy aldehyde, a polyhydroxy ketone, or a compound that
yields polyhydroxy aldehydes or polyhydroxy ketones upon hydrolysis.

Large number of functional groups are present.

 Carbohydrates
 Carbohydrates are classified on the basis of molecular size:
 A monosaccharide is a carbohydrate that contains a single polyhydroxy
aldehyde or polyhydroxy ketone unit.
 Cannot be broken into simpler units by hydrolysis reactions.
 Both glucose and fructose are monosaccharides.
 Three to seven carbon atoms are naturally occurring.
 Five- and six- carbon species are especially common.
 Pure monosaccharides are water-soluble, white, crystalline solids.
 An oligosaccharide is a carbohydrate that contains two to ten monosaccharide
units covalently bonded to each other.
 Disaccharides are the most common type which contains two
monosaccharides units; also crystalline and water soluble-sibstances.
 Sucrose (table sugar) and lactose (milk sugar)
 Within human body, it is often associated with proteins and lipids in
complexes that have both structural and regulatory functions.
 Complete hydrolysis of an oligosaccharide produces monosaccharides.
o Disaccharide produces two monosaccharides.
o Trisaccaride, three monosaccharides.
o Hexasaccharide, six monosaccharides.
 A polysaccharide is a polymeric carbohydrate that contains many
monosaccharide units covalently bonded to each other.
 Contain several thousands of monosaccharide units.
 Both cellulose and starch are polysaccharides.
o Cellulose: Papers, cotton, and wood
o Starch: Foods, bread, pasta, potatoes, rice, corn, beas, and peas

Chirality: Handedness in Molecules

 Most monosaccharides exhibit handedness in two forms.

 Left-handed and Right-handed
 Relationship of mirror images
 Mirror Images
 A mirror image is the reflection of an object in a mirror.
 Two classes:
 Superimposable mirror images are images that coincide at all points when
the images are laid upon each other.
 Nonsuperimposable mirror images are images where not all points
coincide when the images are laid upon each other.
 Human hands are nonsuperimposable thus all objects with nonsuperimposable
mirror images exist in “left-handed” and “right-handed” forms.
 Chirality
 Not all molecules possess handedness.
 Any organic molecule that contains a carbon atom with four different groups
attached to it in a tetrahedral orientation possesses handedness.
 A chiral center is an atom in a molecule that has four different groups
tetrahedrally bonded to it.
 A chiral molecule is a molecule whose mirror images are not superimposable;
have handedness.
 An achiral molecule is a molecule whose mirror images are superimposable; do
not posses handedness.
 Simplest example of chiral monosaccharide:

Bromochloroiodomethane Glyceraldehyde
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 Monosaccharides may contain more than one chiral center.

 Importance of handedness:
 Right-handed and left-handed forms of a molecule often elicit different responses
within the body.
 Sometimes both forms biologically active, each form giving a different response.
 Sometimes both elicit the same response, but one form’s response is many times
greater than that of the other.
 Sometimes only one is biologically active.
 Naturally occurring monosaccharides are almost always “right-handed.”
 Plants, our dietary source for carbohydrates, produce only right-handed
monosaccharides.

Sterioisomerism: Enantiomers and Diastereomers

 The left- and right-handed forms of a chiral molecule are isomers.

 Stereoisomers are isomers that have the same molecular and structural formulas but
differ in the orientation of atoms in space.
 Two major structural features that generate stereoisomerism:
1. Presence of a chiral center in a molecule
2. Presence of “structural rigidity” in a molecule, caused by restricted rotation about
chemical bonds; the basis for cis-trans isomerism.
 Two types:
1. Enantiomers are stereoisomers whose molecules are nonsuperimposable mirror
images. Left- and righ-handed forms of molecule with a single chiral center.
2. Diastereomers are stereoisomers whose molecules are not mirror images of each
other. Cis-trans isomers are diastereomers.

Enantiomers Diastereomers

(a) (b)

 Molecules that contain more than one chiral center can also exist in
diastereomeric as well as enantiomeric forms.

Designating Handedness Using Fischer Projection Formulas

 A Fischer projection formula is a two-dimensional structural notation for showing the

spatial arrangement of groups about chiral centers in molecules.
 A chiral center is represented as the intersection of vertical and horizontal lines thus the
chiral center is not explicitly shown.
1. Vertical lines from the chiral center represent bonds to groups directed into the
printed page.
2. Horizontal lines from the chiral center represent bonds to groups directed out of
the printed page.

 In fischer projection formulas for monosaccharides, the carbon chain is positions

vertically with the carbonyl group at or near the top.
 Glyceraldehyde (2,3-dihydroxypropanal) is the smallest monosaccharide that has a chiral
center.
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 The fischer projection formulas for the two enantiomers of glyceraldehydes are:

L- Glyceraldehyde D- Glyceraldehyde

 The enantiomer with chiral center –OH group on the right in the fischer formula
is by definition the right-handed isomer (D-glyceraldehyde).
 The enantiomer with the chiral center –OH group on the left in the Fischer
projection formula by definition the left-handed isomer (L-glyceraldehyde).
 (2,3,4-trihydroxybutanal), a monosaccharide with four carbons and two chiral centers.

 There are four stereoisomers for this compound-two pairs of enantiomers.

First enantiomeric pair Second enantiomeric pair

 First enantiomeric pair: Both chiral-center –OH groups are on the same side of
the Fischer projection formula.
 Second enantiomeric pair: The chiral center –OH groups are on opposite sides of
the Fischer projection formula.
 The carbon chain is numbered starting at the carbonyl group end of the molecule, and
the highest-numbered chiral center is used to determine D or L configuration.

A B C D

D-erythrose L-erythrose D-threose L-threose

 The D,L nomenclature gives the configuration (handedness) only at the highest-
numbered chiral center.
 A & C, A & D, B & C, B & D are diastereomers/ not mirror images.
 These four pairs are epimers; Epimers are diastereomers whose molecules differ
only in the configuration at one chiral center.

We calculate 2n to predict the maximum possible number of streoisomers for a

molecule with n chiral atoms.

Properties of Enantiomers
 Diastereomers differ in most chemical and physical properties.
 Different boiling points and melting points.
 Enantiomers have nearly identical boiling points and melting points.
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 Enantiomers exhibit different properties in only two areas: (1) their interaction with
plane-polarized and (2) their interaction with other chiral substances.

Interaction of Enantiomers with Plane-Polarized Light

 Ordinary light waves/Unpolarized light waves vibrate in all planes at right angles to their
direction of travel.
 Ordinary light can be converted to plane-polarized light by passing it through a
polarizer, an instrument with lenses or filters containing special types of crystals.
 Plane-polarized light waves vibrate only one place at right angles to their direction of
travel; the direction of travel of the light is toward the reader.
 When plane-polarized light is passed through a solution containing a single
enantiomer, the plane of the polarized light is rotated counterclockwise or
clockwise, depending on the enantiomer.
 Polarimeters are the instruments used to measure the degree of rotation of
plane-polarized light by enantiomeric compounds.

Dextrorotatory and Levorotatory Compounds

 Enantiomers are said to be optically active because of the way they interact with plane-
polarized light. They are often called optical isomers.
 An optically active compound is a compound that rotates the plane of polarized light.
 Achiral molecules are optically inactive.
 Chiral molecules are optically active.
 Dextrorotatory compound is a chiral compound that rotates the plane of polarized light
in a clockwise direction.
 Levorotatory compouns is a chiral compound that rotates the plane of polarized light in
a counterclockwise direction.
 The notation (+) means rotation to the right (clockwise), and (-) means rotation to the
left (counterclockwise)
 Not all D enantiomers rotate plane-polarized light in the same direction, nor do all L
enantiomers rotate plane-polarized light in the same direction.
 Some D isomers are dextrorotatory; others are levorotatory.

Interaction Between Chiral Compounds

 An enantiomeric pair have the same interaction with achiral molecules and different
interactions with chiral molecules.
 Enantiomers have identical boiling points, melting points, and densities because
such properties depend on the strength of intermolecular forces.
 Intermolecular force strength is the same for both forms of chiral
molecule because both forms have identical sets of functional groups.
 A pair of enantiomers have the same solubility in an achiral solvent, such as
ethanol, but differing solubilitites in a chiral solvent, such as D-2-butanol.
 The rate and extent of reaction of enantiomers with another reactant are the
same is the reactant is achiral but differ if the reactant chiral.
 Receptor sites for molecules within the body have chirality associated with them.
 Enantiomers always generate different responses within the human body
as they interact at such sites.
 Sometimes only slightly different, and at other times they are very
different.
o Taste Perceptions
o D-Epinephrine makes a perfect three-point contact with the
receptor surface but the biochemically weaker L-Epinephrine can
make only a two-point contact.
The binding of the L isomer is weaker, and less physiological response is
observed.
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Classification of Monosaccharides
 There is no limit to the number of carbon atoms that can be present in a
monosaccharide.
 Only monosaccharides with three to seven carbon atoms are commonly found in nature.
 Three-carbon: triose
 Four-carbon: tetroses
 Five-carbon: pentoses
 Six-carbon: hexoses
 Monosaccharides are classified as aldoses or ketoses on the basis of type of carbonyl
group present.
 An aldose is a monosaccharide that contains an aldehyde functional group;
Aldoses are polyhydroxy aldehydes.
 A ketose is a monosaccharide that contains a ketone functional group; Ketoses
are polyhydroxy ketones.
 Monosaccharides are also often called sugars thus they have sweet taste; It is a general
designation for either a mono- or disaccharide.

 Trioses are the smallest monosaccharides that can exist in two forms:
1. An aldose (glyceraldehydes)

TRIOSE
(One Chiral Center)

TETROSES
(Two Chiral Center)

Pentoses
(Three Chiral Center)

Hexoses
(Four Chiral Center)
 Carbohydrates

2. A ketose (dihydroxyacetone); Does not possess a chiral carbon atom

 D and L forms are not possible
 Reduces the number of stereoisomers possible for ketotetroses,
ketopentoses, and ketohexoses.
 An aldohexose has four chiral carbon atoms, but a ketose has only three.

TRIOSE

TETROSE

PENTOSES

HEXOSES

Biochemically Important Monosaccharides

 D-Glyceraldehyde and Dihydroxyacetone

 Simplest of the monosaccharides, these two trioses are important intermediates
in the process of glycolysis, a series of reactions whereby glucose is converted
into two molecules of pyruvate.
 D-Glyceraldehyde is a chiral molecule but dihydroxyacetone is not.

 D-Glucose
 It is the most abundant in nature and most important from a human nutritional
standpoint.
 Carbohydrates

 Ripe fruits/grapes are a good source of glucose; grape sugar.

 Two other names are dextrose and blood sugar.
 Optically active; rotates plane-polarized light to the right.
 The normal concentration of glucose in human blood is in the range of 70-100
mg/dL (1dL=100 mL)
 Cells use glucose as a primary source of energy.
 Insulin and glucagon have important roles in keeping glucose blood
concentrations within the normal range.
 Abnormal functioning of the hormonal control process for blood glucose
levels leads to the condition known as diabetes.

L-Glucose is tasteless and the body cannot use it.

 D-Galactose
 D-galactose and D-glucose differ only in the configuration of the –OH group and
–H group on the carbon 4.

 These are epimers.

 D-Galactose is a free monosaccharide.
 Galactose is synthesized from glucose in the mammary glands for use in lactose
(milk sugar), a disaccharide consisting of a glucose unit and a galactose unit.
 D-Galactose is sometimes called brain sugar because it is a component of
glycoproteins found in brain and nerve tissue.
 It is also present in the chemical markers that distinguish various types of blood.

 D-Fructose
 The most important ketohexose.
 Also known as levulose and fruit sugar.
 Naturally occurring D-Fructose rotate plane-polarized light to the left.
 The sweetest-tasting of all sugars.
 Found in many fruits and is present in honey in equal amounts with glucose.
 Sometimes used as dietary sugar because less is needed for the same amount of
sweetness.
 Third to sixth carbon structures are identical of those D-Glucose.
 Differ only in carbon 1 and 2 due to different functional groups.

 D-Ribose
 It is a pentose; If carbon 3 and its groups were eliminated from the structure of
D-Glucose, the remaining structure would be that of D-Ribose.
 Carbohydrates

 D-Ribose is a component of complex molecules, RNAs and energy-rich

compounds such as ATP.
 2-deoxy-D-ribose is also important in nucleic acid chemistry; a component of
DNA. Deoxy means “minus an oxygen”.

Cyclic of Monosaccharides

 Forms Monosaccharides containing five or more carbon atoms, such open-chain

structures are actually in equilibrium with two cyclic structures, and the cyclic structures
are the dominant forms at equilibrium.
 The cyclic forms of monosaccharides result from the ability of their carbonyl group to
react intramolecularly with a hydroxyl group.
 The result is a cyclic hemiacetal.
 Intramolecular cyclization reaction for D-Glucose:

(1) Projection formula: (2) To the right rearrangement: (3) Counterclockwise C-5

(4) C-5 –OH group adds to

(5) carbonyl group

Two isomers are possible, depending on how ring closure occurs.

(6)

Cyclization of glucose (hemiacetal formation) creates a new chiral center at carbon

1, and the presence of this new chiral center produces two stereoisomers, called
alpha and beta.
 A dynamic equilibrium exists:

 Fructose and other ketoses with a sufficient number of carbon atoms also cyclize.
 Carbohydrates

 Galactose, like glucose, forms a six-membered ring, but both D-fructose and D-ribose
form a five membered ring.

 D-Fructose cyclization involves carbon 2 (the keto group) and carbon 5, which
results in two CH2Oh groups being outside the ring (Carbons 1 and 6).
 D-Ribose cyclization involves carbon 1 (the aldehyde group) and carbon 4.
 A cyclic monosaccharide containing a six-atom ring is called pyranose, and one
containing a five-atom ring is called furanose.
 α-D-glucose is a α-D-glucopyranose
 α-D-fructose is a α-D-fructopyranose

Haworth Projection Formulas

 A two dimensional structural notation that specifies the three-dimensional structure of a
cyclic form of a monosaccharide.
 The hemiacetal ring system is viewed “edge on” with the oxygen ring atom at the upper
right (six-membered ring) or at the top (five-membered ring).
 The D or L form of monosaccharide is determined by the position of the terminal CH 2OH
group on the highest-numbered ring carbon atom.
 D form: Positioned above the ring/
 L form: The terminal CH2OH is positioned below the ring.

 In a β configuration, both groups are pointing in the same direction.

 In an α configuration, the two groups are pointing in opposite directions.

 When alpha and beta configuration does not matter, the –OH group on carbon 1 is
placed in a horizontal position, and a wavy line is used as the bond that connects it to
the ring.

 Specific identity of a monosaccharide is determined by the positioning of the other –OH

groups in the Haworth projection formula.
 -OH group to the right in a Fischer projection formula points down in the
Haworth projection formula.
 -OH group to the left in a Fischer projection formula points up in the Haworth
projection formula.
 Carbohydrates

Reactions of Monosaccharides

1. Oxidation to Produce Acidic Sugars

 Monosaccharide oxidation can yield three different types of acidic sugars.
 The oxidizing agent used determines the product.
 Weak oxidizing agents, such as Tollens and Benedict’s solutions, oxidize the
aldehyde end of an aldose to give an aldonic acid.
 Oxidation of the aldehyde end of glucose produces gluconic acid, and
oxidation of the aldehyde end of galactose produces galactonic acid.

 Aldoses acts as reducing agents; they are called reducing sugars.

 With Tollens solution, glucose reduces Ag+ ion to Ag.
 Benedict’s solution, glucose reduces Cu2+ ion to Cu+ ion.
 A reducing sugar is a carbohydrate that gives a positive test with Tollen’s
and Benedict’s solutions.
 Ketoses are also reducing sugars under basic conditions associated with the
solutions above.
 Ketose undergoes a structural rearrangement that produces an
aldose, and the aldose then reacts.

Thus all monosaccharides are reducing sugars.

 Tollen’s and Benedict’s solutions can be used to test for glucose in urine, a
symptom of diabetes.
 Benedict’s solution remains blue if glucose is not present.
 Formation of a red precipitate indicates the presence of glucose.
 Strong oxidizing agents can oxidize both ends of a monosaccharide at the
same time (the carbonyl group and the terminal primary alcohol group) to
produce a dicarboxylic acid; aldaric acids.

 Enzymes can oxidize the primary alcohol end of an aldose such as glucose,
without oxidation of the aldehyde group, to produce an alduronic acid.
Carbohydrates