Carbohydrates

Carbohydrates and their importance:

Carbohydrates can be defined as polyhydroxy alcohols with aldehydes or ketones and their
derivatives.
1. Carbohydrates are the most abundant biomolecules on the earth. each year photosynthesis
converts more than 100 billion metric tons of Carbon dioxide and water into cellulose and
other plant products.
2. the oxidation of Carbohydrates is the central energy-yielding pathway in most non-
photosynthetic cells.
3. carbohydrate polymers serve as structural and protective elements in the cell walls of bacteria
and plants and in the connective tissue of animals.
4. Carbohydrate polymers lubricate skeletal joints and participate in cell-cell recognition and
adhesion.
5. Complex carbohydrate polymers covalently attached to proteins or lipids act as signals that
determine the intracellular destination or metabolic fate of these hybrid molecules, called
glycoconjugates.

Classification of carbohydrates

1. Monosaccharides
2. Disaccharides
3. Oligosaccharides
4. Polysaccharides

A short note about monosaccharides

Monosaccharides, or simple sugars, consist of a single polyhydroxy aldehyde or ketone unit, which
cannot be hydrolyzed into a simple form.
1. The general formula of monosaccharides is Cn (H2 O)n
2. The simple form of aldose is Glyceraldehyde
3. The simple form of ketose is Dihydroxyacetone
4. The common aldose is Glucose
5. The common ketose is Fructose
6. Natural glucose is ᾰ-D-Glucose
Why do Monosaccharides have cyclic structures?
Monosaccharides form cyclic structures because of the ability of the - OH group and an aldehyde or
keto group to react intramolecularly to form a hemiacetal or hemiketal.
***Why triose doesn’t have cyclic structure like other monosaccharides?
Importance of monosaccharides:
1. Carbohydrates are the chief energy source, in many animals, they are an instant source of
energy. Glucose is broken down by glycolysis/ Krebs’s cycle to yield ATP.
2. Glucose is the source of storage of energy. It is stored as glycogen in animals and starch in
plants.
3. Stored carbohydrates act as the energy source instead of proteins.
4. Carbohydrates are intermediates in the biosynthesis of fats and proteins.
5. Carbohydrates aid in the regulation of nerve tissue and is the energy source for the brain.
6. Carbohydrates gets associated with lipids and proteins to form surface antigens, receptor
molecules, vitamins and antibiotics.
7. They form structural and protective components, like in cell wall of plants and
microorganisms.
8. In animals they are important constituent of connective tissues.
9. They participate in biological transport, cell-cell communication and activation of growth
factors.
10. Carbohydrates that are rich in fiber content help to prevent constipation.
11. Also, they help in modulation of immune system.
***Functions of monosaccharides:
Characteristics of Monosaccharides:
1. Monosaccharides are colorless, crystalline solids.
2. Monosaccharides are freely soluble in water and insoluble in nonpolar solvent.
3. Most have a sweet test.
4. All the monosaccharaides except dihydroxyacetone contain one or more asymmetric carbon
atom or chiral carbon. Thus, occur in optical active isomeric forms.
5. In general, molecules with n chiral center can have 2n stereoisomer.
6. The most abundant monosaccharide in nature is the six-carbon sugar D-glucose, sometimes
referred to as dextrose.
7. Monosaccharides of four or more carbons tend to have cyclic structures.
Oligosaccharides
Oligosaccharides consist of short chains of monosaccharide units, or residues, joined by
characteristic linkages called glycosidic bonds. The most abundant are the disaccharides, with two
monosaccharide units. For example, Sucrose consists of the six-carbon sugars D-glucose and D-
fructose.
In cells, most oligosaccharides consisting of three or more units do not occur as free entities but are
joined to non-sugar molecules (lipids or proteins) in glycoconjugates.
***Why the oligosaccharides consisting of three or more monosaccharides unit doesn’t occur as
free entity?
*** Importance of oligosaccharides
*** Functions of oligosaccharides
Polysaccharides
The polysaccharides are sugar polymers containing more than 20 or so monosaccharide units; some
have hundreds or thousands of units. Some polysaccharides, such as cellulose, are linear chains;
others, such as glycogen, are branched. Both cellulose and glycogen consist of recurring units of D-
glucose, but they differ in the type of glycosidic linkage and consequently have strikingly different
properties and biological roles.
Monosaccharides:
The simplest form of the carbohydrates, the monosaccharides, are either aldehydes or ketones with
two or more hydroxyl groups; the six-carbon monosaccharides glucose and fructose have five
hydroxyl groups. Many of the carbon atoms to which the hydroxyl groups are attached are chiral
centers, which give rise to the many sugar stereoisomers found in nature.
*** Why there are so many sugar stereoisomers found in nature?
Why stereoisomerism in monosaccharides is important?
Stereoisomerism in sugars is biologically significant because the enzymes that act on sugars are
strictly stereospecific, typically preferring one stereoisomer to another by three or more orders of
magnitude, as reflected in Km values or binding constants. It is as difficult to fit the wrong sugar
stereoisomer into an enzyme’s binding site.
** The backbones of common monosaccharides are unbranched carbon chains in which all the
carbon atoms are linked by single bonds. In this open-chain form, one of the carbon atoms is
double-bonded to an oxygen atom to form a carbonyl group; each of the other carbon atoms has a
hydroxyl group.
Aldose: If the carbonyl group is at an end of the carbon chain (that is, in an aldehyde group), the
monosaccharide is an aldose.
Ketose: if the carbonyl group is at any other position (in a ketone group), the monosaccharide is a
ketose.
The simplest monosaccharides are the two three-carbon trioses: glyceraldehyde, an aldotriose, and
dihydroxyacetone, a ketotriose.
Monosaccharides with four, five, six, and seven carbon atoms in their backbones are called,
respectively, tetroses, pentoses, hexoses, and heptoses. There are aldoses and ketoses of each of
these chain lengths.
The hexoses, which include the aldohexose D-glucose and the ketohexose D-fructose are the most
common monosaccharides in nature, the products of photosynthesis and key intermediates in the
central energy-yielding reaction sequence in most organisms. The aldopentoses D-ribose and 2-
deoxy-D-ribose are components of nucleotides and nucleic acids.
Trioses: A triose is a monosaccharide, or simple sugar, containing three carbon atoms. The
chemical formula of all trioses is C 3H6O3, and their molecular weight is 90.077 g/mol. There are
only three possible trioses L-glyceraldehyde and D-glyceraldehyde, the two enantiomers of
glyceraldehyde, which are aldotrioses because the carbonyl group is at the end of the chain, and
dihydroxyacetone, the only ketotriose, which is symmetrical and therefore has no enantiomers.
Aldotriose: Glyceraldehyde

Ketotriose: Dihydroxyacetone

Importance of triose: Trioses are important in cellular respiration. During glycolysis, fructose-1,6-
bisphosphate is broken down into glyceraldehyde-3-phosphate and dihydroxyacetone phosphate.
Lactic acid and pyruvic acid are later derived from these molecules.
Tetroses: A tetrose is a monosaccharide with 4 carbon atoms. The chemical formula of all tetroses
is C4H8O4, and their molecular weight is 120.104 g/mol. They have either an aldehyde functional
group in position 1 (aldotetroses) or a ketone functional group in position 2 (ketotetroses).
Aldotetroses: The aldotetroses have two chiral centers and so 4 different stereoisomers are possible
(D- erythrose, L- erythrose, D-threose and L-threose). There are two naturally occurring
stereoisomers, the enantiomers of erythrose and threose having the D configuration but not the L
enantiomers.
Ketotetroses: The ketotetroses have one chiral center and, therefore, two possible stereoisomers:
erythrulose (L- and D-form). Again, only the D enantiomer is naturally occurring.

***Importance of Tetroses:
Pentoses: A pentose is a monosaccharide with five carbon atoms. The chemical formula of all
pentoses is C5H10O5, and their molecular weight is 150.13 g/mol.
Pentoses exist in two forms, open-chain (linear) or closed-chain (cyclic), that easily convert into
each other in water solutions.
Aldopentoses: The aldopentoses have three chiral centers; therefore, eight (23) different
stereoisomers are possible.
Ketopentoses: The 2-ketopentoses have two chiral centers; therefore, four (22) different
stereoisomers are possible. The 3-ketopentoses are rare.

Importance of Pentoses:
Ribose is a constituent of RNA, and the related molecule, deoxyribose, is a constituent of DNA.
Phosphorylated pentoses are important products of the pentose phosphate pathway, most
importantly ribose 5-phosphate (R5P), which is used in the synthesis of nucleotides and nucleic
acids, and erythrose 4-phosphate (E4P), which is used in the synthesis of aromatic amino acids.
Hexose: A hexose is a monosaccharide with six carbon atoms. The chemical formula for all hexoses
is C6H12O6, and their molecular weight is 180.156 g/mol
Hexoses exist in two forms, open-chain or cyclic, that easily convert into each other in aqueous
solutions.
Aldohexoses: In linear form, an aldohexose has four chiral centers, which give 16 possible
aldohexose stereoisomers (24), comprising 8 pairs of enantiomers.

0000 0001

0010 0011
0100 0101

0110 0111
All d-isomers of aldohexoses except d-altrose occur in living organisms, but only three are
common: d-glucose, d-galactose, and d-mannose. The l-isomers of aldohexoses are generally absent
in living organisms; however, l-altrose has been isolated from strains of the bacterium Butyrivibrio
fibrisolvens.
When drawn in this order, the Fischer projections of the d-aldohexoses can be identified with the 3-
digit binary numbers from 0 to 7, namely 000, 001, 010, 011, 100, 101, 110, 111. The three bits,
from left to right, indicate the position of the hydroxyls on carbons 4, 3, and 2, respectively: to the
right if the bit value is 0, and to the left if the value is 1.
Ketohexoses: In the linear form, the 2-ketohexoses have three chiral centers and therefore eight
possible stereoisomers (23), comprising four pairs of enantiomers. The most important example is
fructose.

000 001
010 100
In theory, the ketohexoses include also the 3-ketohexoses, which have the carbonyl in position 3;
namely H–(CHOH)2–C(=O)–(CHOH)3–H, but these compounds are not known to occur in nature,
and are difficult to synthesize.
Monosaccharides Have Asymmetric Centers
All the monosaccharides except dihydroxyacetone contain one or more asymmetric (chiral) carbon
atoms and thus occur in optically active isomeric forms. The simplest aldose, glyceraldehyde,
contains one chiral and therefore has two different optical isomers, or enantiomers.
The structure of biomolecules with chiral centers, the absolute configurations of sugars are known
from x-ray crystallography. To represent three-dimensional sugar structures on paper, we often use
Fischer projection formulas.
***details about Fischer projection.
In general, a molecule with n chiral centers can have 2 n stereoisomers. Glyceraldehyde has 21 = 2;
the aldohexoses, with four chiral centers, have 24 = 16. The stereoisomers of monosaccharides of
each carbon-chain length can be divided into two groups that differ in the configuration about the
chiral center most distant from the carbonyl carbon. When the hydroxyl group on the reference
carbon is on the right (dextro) in a projection formula that has the carbonyl carbon at the top, the
sugar is the D isomer; when on the left (levo), it is the L isomer. Of the 16 possible aldohexoses,
eight are D forms and eight are L. Most of the hexoses of living organisms are D isomers.
***Why most of the hexoses in nature are D isomers?
***Why L isomers of hexoses are absent in nature?
*** Enantiomers in Monosaccharides
The carbons of a sugar are numbered beginning at the end of the chain nearest the carbonyl group.
Each of the eight D-aldohexoses, which differ in the stereochemistry at C-2, C-3, or C-4.
The name fructose comes from the Latin fructus, “fruit”, fruits are one source of this sugar and
sorbose from Sorbus, the genus of mountain ash, which has berries rich in the related sugar alcohol
sorbitol.
Two sugars that differ only in the configuration around one carbon atom is called epimers; D-
glucose and D-mannose, which differ only in the stereochemistry at C-2, are epimers, as are D-
glucose and D-galactose which only differ at C-4.
Some sugars occur naturally in their L form; examples are L-arabinose and the L isomers of some
sugar derivatives that are common components of glycoconjugates.
*** Epimers in monosaccharides
The Common Monosaccharides Have Cyclic Structures
in aqueous solution, aldotetroses and all monosaccharides with five or more carbon atoms in the
backbone occur predominantly as cyclic (ring) structures in which the carbonyl group has formed a
covalent bond with the oxygen of a hydroxyl group along the chain. The formation of these ring
structures is the result of a general reaction between alcohols and aldehydes or ketones to form
derivatives called hemiacetals or hemiketals. Two molecules of an alcohol can add to a carbonyl
carbon; the product of the first addition is a hemiacetal (for addition to an aldose) or a hemiketal (for
addition to a ketose). If the —OH and carbonyl groups are on the same molecule, a five or six-
membered ring results. Addition of the second molecule of alcohol produces the full acetal or ketal,
and the bond formed is a glycosidic linkage. When the two molecules that react are
monosaccharides, the acetal or ketal formed is a disaccharide.
The reaction with the first molecule of alcohol creates an additional chiral center (the carbonyl
carbon). Because the alcohol can add in either of two ways, attacking either the “front” or the
“back” of the carbonyl carbon, the reaction can produce either of two stereoisomeric configurations,
denoted α and β. For example, D-glucose exists in solution as an intramolecular hemiacetal in which
the free hydroxyl group at C-5 has reacted with the aldehydic C-1, rendering the latter carbon
asymmetric and producing two possible stereoisomers, designated α and β.

Isomeric forms of monosaccharides that differ only in their configuration about the hemiacetal or
hemiketal carbon atom are called anomers, and the carbonyl carbon atom is called the anomeric
carbon.
Anomeric relationship between monosaccharides:
Six-membered ring compounds are called pyranoses because they resemble the six-membered ring
compound pyran (Fig. 7-7). The systematic names for the two ring forms of D-glucose are therefore
α-D-glucopyranose and β-D-glucopyranose. Ketohexoses (such as fructose) also occur as cyclic
compounds with α and β anomeric forms. In these compounds, the hydroxyl group at C-5 (or C-6)
reacts with the keto group at C-2 to form a furanose (or pyranose) ring containing a hemiketal
linkage D-Fructose readily forms the furanose ring, the more common anomer of this sugar in
combined forms or in derivatives is β-D-fructofuranose.
Cyclic sugar structures are more accurately represented in Haworth perspective formulas than in the
Fischer projections commonly used for linear sugar structures. In Haworth perspectives, the six-
membered ring is tilted to make its plane almost perpendicular to that of the paper, with the bonds
closest to the reader drawn thicker than those farther away.
Details about Haworth perspective formula.