CARBOHYDRATE

 large group of organic compounds

 occurring in foods and living tissues and including sugars, starch, and cellulose.
 contain hydrogen and oxygen in the same as water (2:1)
 can be broken down to release energy in the animal body
 polyhydroxyaldehyde or polyhydroxyketone
 a substance that gives these compounds on hydrolysis.

 Also known as saccharide-meaning sugar (The word saccharide comes from

the Greek word σάκχαρον (sákkharon), meaning "sugar".)

 The major source of carbohydrates in the body is from dietary intake of plant materials

Classifications:

1. According to number of units

- monosaccharides, disaccharides, oligosaccharides, polysaccharides

2. According to reducing property

- Reducing and non-reducing sugars

3. According to the number of carbons in a unit

- Hexose, pentose, tetrose….

• Monosaccharide: a carbohydrate that cannot be hydrolyzed to a simpler carbohydrate.

– Monosaccharides have the general formula C nH2nOn, where n varies from 3 to 8.

– Aldose: a monosaccharide containing an aldehyde group.

– Ketose: a monosaccharide containing a ketone group.

– Classified by their number of carbon atoms

Name Formula
Triose C3 H6 O3
Tetrose C4 H8 O4
Pentose C5 H1 0 O5
Hexose C6 H1 2 O6
• There are only two trioses:
CHO CH2 OH Heptose C7 H1 4 O7
CHOH C= O
CH2 OH CH2 OH
Octose C8 H1 6 O8
Glyceraldehyde Dihydroxyacetone
(an aldotriose) (a ketotriose)
 – Often aldo- and keto- are omitted and these compounds are referred to simply as
trioses.

– Although “triose” does not tell the nature of the carbonyl group, it at least tells the
number of carbons.

The simplest aldose: Glyceraldehyde - contains a stereocenter and exists as a pair of enantiomers.

• Fischer projection: a two dimensional representation for showing the configuration of

tetrahedral stereocenters.

– Horizontal lines represent bonds projecting forward from the stereocenter.

– Vertical lines represent bonds projecting to the rear.

– Only the stereocenter is in the plane.

– -Dmonosaccharide: the -OH on its last chiral carbon is on the right in a Fischer
projection.

– L-monosaccharide: the -OH on its last chiral carbon is on the left in a Fischer
projection.

The most common D-tetroses and D-pentoses are:

o D-Eryhtrose, D- Threose, D-Ribose, 2-Deoxy-D-ribose

The three most common D-hexoses are:

o D-Glucose, D-Galactose, D-Fructose

Isomers of monosaccharides:

1. Enantiomers

2. Diastereomers

3. Epimers

4. Anomers

5. Optical isomers

Projections:

1. Fischer

2. Haworth

• Haworth
 • Aldehydes and ketones react with alcohols to form hemiacetals.

– Cyclic hemiacetals form readily when the hydroxyl and carbonyl groups are part of
the same molecule and their interaction can form a five- or six-membered ring.

– A five- or six-membered cyclic hemiacetal is represented as a planar ring, lying

roughly perpendicular to the plane of the paper.

– Groups bonded to the carbons of the ring then lie either above or below the plane of
the ring.

– The new carbon stereocenter created in forming the cyclic structure is called an
anomeric carbon.

– Stereoisomers that differ in configuration only at the anomeric carbon are called
anomers.

– The anomeric carbon of an aldose is C-1; that of the most common ketoses is C-2.

• In the terminology of carbohydrate chemistry,

– b means that the -OH on the anomeric carbon is on the same side of the ring as the
terminal -CH2OH.

– a means that the -OH on the anomeric carbon is on the side of the ring opposite
from the terminal -CH2OH.

– A six-membered hemiacetal ring is called a pyranose, and a five-membered

hemiacetal ring is called a furanose.

– Aldopentoses also form cyclic hemiacetals.

– The most prevalent forms of D-ribose and other pentoses in the biological world are
furanoses.

– The prefix “deoxy” means “without oxygen.

3. Dreiding

Chair Conformations

• For pyranoses, the six-membered ring is more accurately represented as a chair

conformation.

• In both Haworth projections and chair conformations, the orientations of groups on

carbons 1- 5 of b-D-glucopyranose are up, down, up, down, and up.

Mutarotation

• Mutarotation: the change in specific rotation that accompanies the equilibration of a- and b-
anomers in aqueous solution.
Physical Properties

• Monosaccharides are colorless crystalline solids, very soluble in water, but only slightly
soluble in ethanol
Sweetness Sweetness
• Sweetness relative to sucrose: Relative to Artificial Relative to
Carbohydrate Sucrose Sweetener Sucrose
fructose 1.74 saccharin 450
sucrose (table sugar) 1.00 acesulfame-K 200
honey 0.97 aspartame 180
glucose 0.74
maltose 0.33
galactose 0.32
lactose (milk sugar) 0.16

Derivatives
of
Monosaccharides

• Treatment of a monosaccharide, all of which exist almost exclusively in cyclic hemiacetal

forms, with an alcohol gives an acetal.

Storage forms of inactive sugars in plants which is activated for use by certain
enzymes.

Glycosides

-A cyclic acetal derived from monosaccharide (e.g digitalin)

-The bond from the anomeric carbon to the -OR group is called a glycosidic bond.

-a compound formed from a simple sugar and another compound by replacement of a hydroxyl
group in the sugar molecule.

-Mutarotation is not possible in a glycoside because an acetal, unlike a hemiacetal, is not in

equilibrium with the open-chain carbonyl-containing compound.

• are stable in water and aqueous

base, but like other acetals, are

hydrolyzed in aqueous acid to an

alcohol and a monosaccharide.

• many drugs and poisons derived from

Plants are glycosides.

• are named by listing the alkyl or aryl group bonded to oxygen followed by the name of the
carbohydrate in which the ending -e is replaced by -ide.
 Reduction to Alditols/Glucitols
(sugar alcohols)
Widely used in the food industry as sweeteners and thickeners

• The carbonyl group of a monosaccharide can be reduced to a hydroxyl group by a variety of

reducing agents, including NaBH4 and H2 in the presence of a transition metal catalyst.

– The reduction product is called an alditol.

Alditols
– Sorbitol is found in the plant world in many berries and in cherries, plums, pears,
apples, seaweed, and algae.

– It is about 60 percent as sweet as sucrose (table sugar) and is used in the

manufacture of candies and as a sugar substitute for diabetics.

– These three alditols are also common in the biological world.

(unlike sugars, which tend to exist as rings, sugar alcohols do not.)

Oxidation to Sugar Acids (Aldonic Acids)

– The aldehyde group of an aldose is oxidized under basic conditions to a carboxylate

anion.

– The oxidation product is called an aldonic acid.

– A carbohydrate that reacts with an oxidizing agent to form an aldonic acid is

classified as a reducing sugar (it reduces the oxidizing agent).

Uses of gluconic acid

• Gluconic acid occurs naturally in fruit, honey, and wine.

• As a food additive it is an acidity regulator.

• It is also used in cleaning products where it dissolves mineral deposits especially in alkaline
solution. (The gluconate anion chelates Ca 2+, Fe2+, Al3+, and other metals.)

Oxidation to Uronic Acids

• Enzyme-catalyzed oxidation of the primary alcohol at C-6 of a hexose yields a uronic acid.

– Enzyme-catalyzed oxidation of D-glucose, for example, yields D-glucuronic acid.

D-Glucuronic Acid

– D-Glucuronic acid is widely distributed in the plant and animal world.

– In humans, it is an important component of the acidic polysaccharides of connective

tissues.
 – It is used by the body to detoxify foreign phenols and alcohols; in the liver, these
compounds are converted to glycosides of glucuronic acid and excreted in the urine.

Aldaric acids

Aldaric acids-are produced when a strong oxidizing agent oxidizes both ends of a monosaccharide,
the aldehyde and alcohol groups to carboxylic acid.

• cannot form cyclic hemiacetals like unoxidized sugars, but they can sometimes

form lactones.

Amino sugars

• contain an -NH2 group in place of an -OH group.

– Only three amino sugars are common in nature: D-glucosamine, D-mannosamine,

and D-galactosamine.

Phosphate Esters

• Mono- and diphosphoric esters are intermediates in the metabolism of monosaccharides.

– For example, the first step in glycolysis is conversion of D-glucose to a-D-glucose 6-

phosphate.

– Note that at the pH of cellular and intercellular fluids, both acidic protons of a
diphosphoric ester are ionized, giving it a charge of -2.

Functions of Carbohydrates
1. Structure: cellulose, chitin, alginate, pectin
2.Energy storage(starch, glycogen )
3. Immediate source of energy
4. Transport
5. Regulatory
6. Catalytic
7. Antigen-antibody interactions immunoglobulins
8. Filtration barriers
9. Cell lubrication
10. Components of cellular membrane, clotting proteins, and protective cellular coats

 Provides energy- immediate source of glucose

 Provides carbon atoms for other biochemical substances
 Part of the framework of DNA and RNA
 Link to lipids as structural component of the cell membrane
Disaccharides
• Sucrose (table sugar)
– Sucrose is the most abundant disaccharide in the biological world; it is obtained
principally from the juice of sugar cane and sugar beets.

– Sucrose is a nonreducing sugar.

• Lactose

– Lactose is the principal sugar present in milk; it makes up about 5 to 8 percent of

human milk and 4 to 6 percent of cow's milk.

– It consists of D-galactopyranose bonded by a b-1,4-glycosidic bond to carbon 4 of D-

glucopyranose.

– Lactose is a reducing sugar.

• Maltose

– Present in malt, the juice from sprouted barley and other cereal grains.

– Maltose consists of two units of D-glucopyranose joined by an a-1,4-glycosidic bond.

– Maltose is a reducing sugar.

Cellobiose

• a disaccharide with the formula [HOCH2CHO(CHOH)3]2O. Cellobiose, a reducing sugar,

consists of two β-glucose molecules linked by a β(1→4) bond. It can be hydrolyzed
to glucoseenzymatically or with acid.

Polysaccharides
• carbohydrate consisting of large numbers of monosaccharide units joined by glycosidic
bonds.

• Starch: a polymer of D-glucose.

• Starch can be separated into amylose and amylopectin.

• Amylose is composed of unbranched chains of up to 4000 D-glucose units joined by

a-1,4-glycosidic bonds.

• Amylopectin contains chains up to 10,000 D-glucose units also joined by a-1,4-

glycosidic bonds; at branch points, new chains of 24 to 30 units are started by a-1,6-
glycosidic bonds.

• Glycogen is the energy-reserve carbohydrate for animals.

• Glycogen is a branched polysaccharide of approximately 10 6 glucose units joined by

a-1,4- and a-1,6-glycosidic bonds.

• The total amount of glycogen in the body of a well-nourished adult human is about
350 g, divided almost equally between liver and muscle.
 • Cellulose is a linear polysaccharide of D-glucose units joined by b-1,4-glycosidic bonds.

• It has an average molecular weight of 400,000 g/mol, corresponding to

approximately 2200 glucose units per molecule.

• Cellulose molecules act like stiff rods and align themselves side by side into well-
organized water-insoluble fibers in which the OH groups form numerous
intermolecular hydrogen bonds.

• This arrangement of parallel chains in bundles gives cellulose fibers their high
mechanical strength.

• It is also the reason why cellulose is insoluble in water.

 linear polymer containing as many as 3000 units of D-glucose joined by b-1,4-glycosidic

bonds.

• Cellulose (cont’d)

– Humans and other animals cannot use cellulose as food because our digestive
systems do not contain b-glucosidases, enzymes that catalyze hydrolysis of b-
glucosidic bonds.

– Instead, we have only a-glucosidases; hence, the polysaccharides we use as sources

of glucose are starch and glycogen.

– Many bacteria and microorganisms have b-glucosidases and can digest cellulose.

– Termites have such bacteria in their intestines and can use wood as their principal
food.

– Ruminants (cud-chewing animals) and horses can also digest grasses and hay.

Acidic Polysaccharides

• Acidic polysaccharides: a group of polysaccharides that contain carboxyl groups and/or

sulfuric ester groups, and play important roles in the structure and function of connective
tissues.

– There is no single general type of connective tissue.

– Rather, there are a large number of highly specialized forms, such as cartilage, bone,
synovial fluid, skin, tendons, blood vessels, intervertebral disks, and cornea.

– Most connective tissues are made up of collagen, a structural protein, in

combination with a variety of acidic polysaccharides.

• Hyaluronic acid

– contains from 300 to 100,000 repeating units.

– is most abundant in embryonic tissues and in specialized connective tissues such as

synovial fluid, the lubricant of joints in the body, and the vitreous of the eye where it
provides a clear, elastic gel that maintains the retina in its proper position
 • Heparin: a heterogeneous mixture of variably sulfonated polysaccharide chains, ranging in
molecular weight from 6,000 to 30,000 g/mol.

• Heparin (cont’d)

– Heparin is synthesized and stored in mast cells of various tissues, particularly the
liver, lungs, and gut.

– The best known and understood of its biological functions is its anticoagulant
activity.

– It binds strongly to antithrombin III, a plasma protein involved in terminating the

clotting process.

Glycoconjugates: Proteoglycans

• are proteins that are heavily glycosylated.

• The basic proteoglycan unit consists of a "core protein" with one or more covalently
attached glycosaminoglycan (GAG) chain(s).

• The point of attachment is a serine (Ser) residue to which the glycosaminoglycan is joined
through a tetrasaccharide bridge (e.g. chondroitin sulfate-GlcA-Gal-Gal-Xyl-PROTEIN).

Glycoconjugates: peptidoglycans

• a polymer that is composed of polysaccharide and peptide chains, forms a mesh-like layer
outside the plasma membrane and is found especially in bacterial cell walls—called also
mucopeptide, murein.

• The sugar component consists of alternating residues of β-(1,4) linked N-acetylglucosamine

and N-acetylmuramic acid.

Nucleic Acids