Carbohydrates

2.0 CARBOHYDRATES
2.0 Introduction to Carbohydrates
• Carbohydrates (CH2O)n are polyhydroxy ketones or polyhydroxy aldehydes
• The -OH groups allow CHO to participate in hydrogen bonding
• CHO are optically active (contain at least one chiral carbon)
• Derivatives of CHO in cells comprise of glyco-lipids (CHO combined with lipids) and
glyco-proteins (CHO combined with proteins)
• Summary of carbohydrate functions:
Oxidation of carbohydrates yields energy
Polysaccharides provide structure to cells
Glycolipids and glycoproteins are involved in signaling processes, cell-cell
interactions and inmunological responses

2.1 Cassification of carbohydrates

'Saccharide' (Latin word for sugar) is the basis for the system of carbohydrate
classification
Glycerol (considered the parent compound although it is not a carbohydrate itself) can be
oxidized to the aldehyde (glyceraldehyde) or ketone (dihydroxy acetone) forms, which
form the bases for all carbohydrates
• Monosaccharides are simple CHO (do not cleave to smaller carbohydrates when
hydrolysed)
• Disaccharides are a combination of only two monosaccharide units (linked by
glycosidic bonds)
• Oligosaccharides consist of 3-10 mono- saccharide units (linked by glycosidic
bonds)
• Polysaccharides consist of more than 10 monosaccharide units (may be up to
thousands)

2.2 Monosaccharides
2.2.1 Nomenclature and stereochemistry
Monosaccharides (and disaccharides) are named using the '-ose' termination
- Aldoses are CHO containing an aldehyde
eg Glyceraldehyde is an aldotriose (aldose with 3C's)
- Ketoses are CHO containing a ketone
eg Dihydroxyacetone is a ketotriose (ketose with C's)
#of Aldoses Ketoses
C's Name Isomers Name Isomers
3 Aldotriose 2 Ketotriose 1
4 Aldotetrose 4 Ketotetrose 2
5 Aldopentose 8 Ketopentose 4
6 Aldohexose 16 Ketohexose 8
* Check out names and structures of monosaccharides for yourself in most Organic
Chemistry books

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- Glyceraldehyde is the simplest carbohydrate

Carbon-2 of glyceraldehyde is a chiral center and thus the molecule exists in
two conformations or enantiomers

The Fischer projections indicate the stereo-chemistry of each chiral center (Groups to the
left and right come out of the plane, the groups above and below are into the plane)
- Consider the structure of D-glucose

- The chiral C farthest from the most oxidized carbon (aldehyde or ketone moeity)
determines if it is a D or L enantiomer
D configuration: the hydroxyl points to the right
L configuration: the -OH group points to the left
The D isomers are more useful biologically
- Epimers are CHO that differ only in their stereochemistry at one position (eg
Glucose and mannose differ at C-2; glucose and galactose differ at C-4)
2.2.2 Cyclization of sugars
Aldoses or ketoses react (intramolecular reaction) to form hemiketals (6-C rings) or
hemiacetals (5-C)
[Structures are better drawn in Haworth projections because the Fischer projection looks
complicated]

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- Six-member rings resemble pyran (more stable) and are referred to as

pyranosides
- Five-member rings resemble furan and are referred to as furanosides

- Anomers are the different stereoisomers of α and β structures

The aldehyde or ketone carbon is referred to as the anomeric carbon (as this is
the chiral center that differs between 2 anomers)
For D-sugars, the α anomer has the hydroxyl group down in the Haworth
projection (and on the same side as the ring oxygen in the Fisher projection)

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- Mutarotation ia a process by which different anomers interconvert in solution

(the process of equilibrates the ratios of α and β anomers - 1/3 α-D-glucopyranose :
2/3 β-D-glucopyranose)

- In D-glucose, the β anomer is more stable because the C1 -OH group is

equatorial
The chair form is more stable than the boat form
The molecules adopt these stable forms to reduce steric clashes between the
ring sub-stituents, and between larger substituents in the equatorial position

2.2.3 Reducing sugars

An aldose is a reducing sugar that oxidizes to a carboxylic acid in the presence of
mild oxidizing agents (eg Cu2+ or Fe3+ in Fehlings and Benedicts reagents ie basic rxns
used for quantitating glucose)
eg. R-CHO + 2Cu2+ + 5OH- –> R-CO2- + Cu2O + 3H2O
Visualized as deposition of red Cu2O

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2.2.4 Hexose derivatives

In biochemistry, enzymes modify sugars by the following methods:
Capping of a hydroxyl by certain chemical group (eg phosphate and sulfate)

Changing of one of the hydroxyl for a nitrogen

Oxidation of one of the aldehydes or alcohols to an acid

(i) Oxidation of the C1 aldehyde produces aldonic acids:

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(ii) Oxidation of the C6 alcohol produces uronic

acids:

2.3 Disaccharides
Disaccharides are two monosaccharides linked by a glycosidic bond (glycosidic
bonds are formed between the anomeric carbon and an alcohol)

The name of the glycoside specifies the two monosaccharides and the glycosidic
linkage

Common disaccharides
Common name Glycoside and linkage
Lactose galactose β(1,4) glucose
Gal β(1,4) Glc (Abbreviation)
Sucrose glucose α(1,2) β-fructose
(non reducing) Glc α(1,2) β-Fru
Trehalose glucose α(1,1) α-glucose
(non reducing) Glc α(1,1) α-Glc
Maltose glucose α(1,4) glucose
Glc α(1,4) Glc
Cellobiose glucose β(1,4) glucose
Glc β(1,4) Glc
The configuration (α or β) is specified for the anomeric carbon used in the linkage for sucrose
and trehalose

• Lactose = glucose + galactose (aka milk sugar)

β-D-galactopyranosyl(1→4)-D-glucopyranose
Gal β(1,4) glc
- Galactose is in the β configuration, C#1 (anomeric C) of galactose is linked to C-4 of
glucose
- Lactose is a reducing sugar because of the 'free' C#1 of the glucose moiety
- Lactose is associated with lactose intolerance (an intestinal distress caused by a
deficiency of the enzyme lactase to digest lactose in milk)
•

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Sucrose = glucose + fructose (aka saccharose or table sugar)

- The main ingredient in cane juice, brown/table sugar

- Invert sugar is a term for the mixture of glucose and fructose found in fruits
• Trehalose (sugar in fungi) and cellobiose are structurally related to maltose but
with different linkages

• Maltose = 2 glucose (aka malt sugar)

Glucose α(1,4) glucose

2.4 Polysaccharides
Homopolysaccharides are composed of single monosaccharide building blocks
Heteropolysaccharides are composed of more than one type of monosaccharide
(Hydrolysis is the rxn in which water is used to break long polysaccharide chains into smaller
units)
The following common polysaccharides play important roles in nutrition and
biology:

Starch
Starch is the major ‘stored CHO’ in plants
These are α(1,4)-linked glucose polymers that are periodically branched with α
(1,6)-linkages

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- Modified starch is starch that has been changed by mechanical processes or chemical
treatments to stabilize starch gels made with hot water (Without modification gels lose
viscosity or become rubbery)
- Hydrogenated glucose syrup is produced by hydrolyzing starch, and then hydrogenating
the syrup to produce sugar alcohols like maltitol and sorbitol

- Natural starch is a mixture of

(i) 10-20% amylose (linear α-D-Glucose polysaccharides which form a colloid
in
hot water)
(ii) 80-90% amylopectin (highly branched and insoluble polysaccharides)

- Amylose molecules consist typically of 200 – 20,000 glucose units which form a
helix

- Amylopectins are highly branched structures of ≅ 30 glucose units attached to

approximately every 20-30 glucose units along the chain (may contain up to two
million glucose units)

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Glycogen
- Glycogen is the major stored CHO in animals and human
- Glycogen has polymer branches of α-D-Glucose of ≅ 13
glucose units (almost similar but smaller than amylopectin)

- Glucose is stored as glycogen in animal tissues by the process of glycogenesis

Cellulose
Cellulose is a polymer of β-D-Glucose oriented with -CH2OH groups alternating
above and below the plane of the cellulose molecule

- Cellulose is the major structural material of plants

(The absence of side chains allows cellulose molecules to lie close and form rigid
structures)
- It can be hydrolyzed (digested) to its constituent glucose units by microorganisms that
inhabit the digestive tract of termites and ruminants (but it is
not digestible by humans)

Chitin
Chitin is an unbranched polymer of N-Acetyl-D-glucosamine (a derivative of
cellulose)
It is the principal component of arthropod and lower animal exoskeletons eg
shells of insects, crabs and shrimps

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Pectin
Pectin is a polymer of α-Galacturonic acid with a variable number of methyl ester
groups

- Pectin acts as a ‘cementing material’ in the cell walls of plant tissues

The white portion of the rind of lemons and oranges contain ≈30% pectin
Pectin is important in the food industry – used as a thickener in fruit preserves, jellies
and jams

2.5 Other common linkages to polysaccharides

2.6 Blood glucose test (using enzyme)

The rapid glucose test used to manage the
levels of glucose in ‘diabetes mellitus’ patients
is described in the following two reactions:
(i) Oxidation of glucose (reducing sugar)
- The enzyme glucose oxidase catalyzes the oxidation of β-D-glucose to D-
gluconic acid using O2 (from the air) as the oxidizing agent (The α-D-glucose is
rapidly converted to the β form so that all of the glucose is measured at one time)

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- During the reaction the ring opens and the aldehyde on carbon #1 is
converted to the D-gluconic acid and the O2 (in the presence of water) is
converted to H2O2

(ii) Color producing reaction

- Ortho-toluidine or 2-methylaniline reacts with the H2O2 using the enzyme
peroxidase to produce a colored chemical
- The concentration of glucose is related to the intensity of color produced

2.7 Iodine test for starch

When starch is mixed with iodine (in water) an intense blue colored starch-iodine
complex is formed by the following mechanism:
(i) The iodine (in the form of I5- ions) slips into the coils of
the β-amylose
(ii) The iodine molecules and are forced into a linear form of
arrangement
(iii) charge transfer (between the starch and the iodine) leads to
the formation of a colored complex

2.8 Carbohydrate metabolism (An overview)

- Carbohydrate metabolism is central to all metabolic processes
- Glucose is metabolized by a stepwise oxidative process accomplished either
anaerobically or aerobically, resulting in the synthesis of adenosine
triphosphate (ATP)
- Glucose is phosphorylated to G-6-P
- Conversion of G-6-P to glycogen is reversible through glycogenesis and
glycogenolysis
- Oxidization of G-6-P to to pyruvate and visa-versa is achieved through
glycolysis and gluconeogenesis
- Pyruvate can be reversibly converted to lactate and can be converted to acetyl
CoA which enters into the the Citric Acid Cyle (aka Tricarboxylic Carboxylic Acid
Cycle or Krebs Cycle)
- The process of anaerobic glucose metabolism results in the net formation of
ATP

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