CARBOHYDRATES

Carbohydrate - Ability of a stereoisomer to rotate plane-

- polyhydroxylaldehyde/polyhydroxyketone
polarized

- Substances that gives these compounds on - Measured by the polarimeter

hydrolysis:
- Light can be rotated

• Monosaccharides
• Clockwise - dextrorotatory (+)

• Oligosaccharides
• Counter-clockwise - levorotatory (-)

glycosidic bond
• Polysaccharides

(poly & oligosacch. produce monosacch. through Fischer Projection Formulas (linear)
hydrolysis by breaking glycosidic bond) - 2D structural notation of showing spatial
arrangement of groups about chiral centers in
Monosaccharide molecules

- Cannot be hydrolyzed to a simpler • Horizontal - bonds projecting forward from

carbohydrate
stereocenter

- CnH2nOn where n varies from 3 to 8

• Vertical - projecting to the rear

• Aldose

- aldehyde; polyhydroxyaldehyde
D-mono: -OH on its penultimate is on the right in
- More than 1 hyrdroxyl group
a Fischer projection

- Triose = 3 carbon sugar

L-mono: -OH on its penultimate is on the left in a
• Ketose - ketone grp; polyhydroxyketone
Fischer projection

ex.:

Oligosaccharide
- 2 to 10 monosaccharide units covalently
bonded to each other

• Dissacharide

- 2 monosaccharide units covalently bonded

to each other

- Most abundant oligosaccharide

• Polysaccharide - polymeric carbo. w/ more

than 10 monosaccharide units bonded to
each other; usually thousands
There are only 2 trioses:

Chirality - the mirror image of the right hand is

the left hand
Simplest aldose;
Simplest ketose:

aldotriose Ketotriose;

• Chiral center - atom in a molecule that has 4 Only sugar not

different groups tetrahedrally handed to it
optically active
• Chiral molecule - molecule whose mirror
images are not superimposable.

Monosacch. classified by no of carbon atoms

Stereoisomers - isomers that have some
molecular and structural formulas but different in Triose C3H6O3 1 chiral carbon
the orientation of atoms in space
Tetrose C4H8O4 2 chiral carbon
• Enantiomers - non-superimposable mirror
Pentose* C5H10O5 3 chiral carbon
images

Hexose* C6H12O6 4 chiral carbon

• Diastereomers - non-superimposable not Heptose C7H14O7 5 chiral carbon
mirror images

Octose C8H16O8 6 chiral carbon

Optical activity * - most abundant

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 CARBOHYDRATES

Examples of Fischer and Haworth projection:

D-glucose:

a-D-fructofuranose

Fischer Abbreviated Haworth

b-D-fructofuranose

/glucopyranose
Aldohexoses = pyranose

Aldopentoses

D-allose:
Ketohexoses
= furanose
Haworth Projection Formulas

- 5 or 6 membered cyclic hemiacetal is

represented as 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

a-D-allose/ b-D-allose/
allopyranose Allopyranose • Anomeric carbon - new carbon stereoisomer
created in forming cyclic structures

D-allose

D-ribose:

• Anomers - stereiosomers differ in

configuration only at the anomeric carbon

C-1 = a. carbon of aldose

a-D-ribofuranose b-D-ribofuranose C-2 = carbon for common ketose

- β = OH is same side of the CH2OH

- α = OH opposite side of CH2OH

D-arabinose: - Pyranose - 6-membered hemiacetal ring

- Furanose - 5-membered hemiacetal ring

- Aldopentoses form cyclic hemiacetals

- Most prevalent forms of D-ribose and other

pentoses in the biological world are furanoses

b-D-arabifuranose
- “Deoxy” = without oxygen

a-D-arabifuranose

D-fructose:

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 CARBOHYDRATES

- D-fructose (2-ketohexose) forms 5-membered ➡ D-glucose — D-gluconic acid (COOH)

cyclic hemiacetal
— D-gluconate (COO-)

➡ D-ribose — D-ribonic acid

(CHO) (COOH)
Biologically Important Monosaccharides
Glucose, Fructose, Galactose and Ribose

Glucose
- Most common carbohydrate; aldohexose

- Reducing sugar

- “Dextrose” bc dextrorotatory

- “Blood sugar” bc it circulates in blood at D-ribose to D-ribonic acid

65-100mg/ml of blood

- Energy source
Oxidation to Aldaric Acids (Strong) - HNO3
- Gluconeogenesis - In animals, glucose - Secondary alcohols DON’T get oxidized by
synthesized in liver and kidneys from non- this reagent (nitric acid)

carbohydrate intermediates by a process

➡ Aldose — Aldaric acid

(COOH)
Fructose (fruits and honey)
- Commonly found w/ glucose and sucrose in

honey

- Reducing sugar
HNO3
- Most important ketose sugar

- “Levulose” bc levorotatory

- Sweeter than glucose

- Very low glycemic index (GI) compared to

(COOH)
sucrose

Galactose
➡ D-ribose — D-ribaric acid

- Component of dissacharide lactose/milk sugar

- Must be converted into a phosphorylated form

of glucose, which is then used in cellular



metabolic rxns.

- Galactosemia = absence of enzymes in the HNO3

conversion of phosphorylated form.

- D-galactose in its modified form,

- B-D-N acetylagalactosamine are components

of blood group antigens

Oxidation of Monosaccharides
Oxidation to Aldonic Acids (Mild) - Cu^2+
- Aldehyie group of aldose is oxidized under COOH
basic conditions to a carboxylate anion

- “Aldonic acid” - oxidation product

- Reducing sugar - carbohydrate that reacts w/

oxidizing agent to form an aldonic acid

‣ ex.: Benedict’s reagent reduces the

oxidizing agent

➡ Aldose — Aldonic acid

COOH

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 CARBOHYDRATES

Mild Reduction Lactose (galactose + glucose)

- Reduction = “Hydrogenation”
- Sugar found in milk

➡ Aldose — alditol
- 5-8% of human milk; 4-6% of cow’s milk

➡ D-ribose — D-ribitol
- Made up of D-galactose and D-glucose linked
by a β(1—4) glycosidic linkage

- Reducing sugar

b-D- b-D-
galactose glucose

Biologically Important Dissacharides LACTOSE

Maltose, Lactose, and Sucrose

Maltose

- Malt sugar
(1—4)
glycosidic
- Made up of two D-glucose units linked by an α b-D- bond
galactopyranosyl b-D-
(1—4) glycosidic linkage
(1—4) glucopyranose
- Reducing sugar

Sucrose
- Table sugar, can sugar, beet sugar

- Most abundant dissacharide in the biological

world

- Obtained principally from the juice of

sugarcane and sugarbeet

- Made up of α -D-glucose and β -D-fructose

linked by a β(1—2) glycosidic linkage

MALTOSE - NON-reducing sugar

a(1—4)
Glycosidic
bond

a-D- a-D-
glucopyranosyl-(1—4) glucopyranoside

➡ α(1—4)

➡ α-D-glucose

➡ Glycosidic acid

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 CARBOHYDRATES

Blood Group Antigens

- Total amount of glycogen in the body of a well-
- Blood group determinant is found at the non- nourished adult human is about 350g, divided
reducing end of an oligosaccharide chain equally between muscle and liver

attached to lipid or protein on the RBC

membrane
Cellulose

‣ O-Antigen — N-acetylglucosamine
- Linear polysaccharide of D-glucose units
‣ A-Antigen — N-acetylgalactosamine
joined by β-1,4-glycosidic bonds

‣ B-Antigen — Galactose
- Structural component of plant cell walls

‣ A and B — Both A and B antigens

- Most abundant naturally occuring
- Agglutination - Antigen/antibody reacting to polysaccharide

blood
- Has average molecular weight of 400,000 g/
mol, corresponding to approximately 2200
Polysaccharides glucose units per molecule

- carbohydrate consisting of large numbers of - Acts like stiff rods and align themselves side
monosaccharide units joined by glycosidic by side into well-organized water-insoluble
bond
fibers

Classifications Based on Function - Parallel chains in bundles gives cellulose fibers

- Storage Polysaccharide
their high mechanical strength

‣ Storage form of monosaccharide is used - Humans and other animals cannot use
as energy source in cells
cellulose as food because our digestive
‣ ex.: starch, glycogen
systems do not contain β-glucosidases
- Structural Polysaccharide
enzymes (catalyze hydrolysis of β-glucosidic
‣ Senses a structural element in plant cell bond)

walls and animal exoskeleton

- We only have α -glucosidases—hence, the
‣ ex.: cellulose, chitin

polysaccharides we use as sources of glucose

are starch and glycogen

Starch - Many bacteria and microorganisms have β-

- Made of monomer D-glucose

glucosidases and can digest cellulose

- Energy storage in plants

- Termites have such bacteria in their intestines
- Consists of amylose (linear polysacch) and
and can use wood as their principle food

amylopectin (branched polysacch)

- Ruminants (cud-chewing animals) and horses
- Amylose is composed of unbranched chains of can also digest grass and hay

up to 4000 D-glucose units joined by α -1,4- - Rumen — horses special stomach

glycosidic bonds

- Amylopectin contains chains up to 10,000 D- Acidic Polysaccharides

glucose units also joined by α -1,4-glycosidic - Polysaccharide with a disaccharide repeating

bonds;
units which one of the disaccharide
- At branch points, new chains of 24 to30 units components is an amino sugar and one or
are started by α-1,6-glycosidic bonds
both disaccharide components has a negative
charge due to a sulfate group or carboxyl
Glycogen group

- Made of monomer D-glucose

- Glycosaminoglycans (GAGs)

- Energy storage in humans and animals

- Mucopolysaccharide

- Branched polysaccharide of approximately - Play important roles in the structure and

10^6 glucose units joined by α-1,4- and α-1,6- function of connective tissues

- Include hyaluronic acid, heparin, chondroitin

glycosidic bonds;

- sulfate, keratan sulfate etc.

Amylopectin structure

- Good shock absorber

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 CARBOHYDRATES

Hyaluronic Acid
- Consists of alternating residues of N-acetyl-β-
D-glucosamine and D-glucuronic acid

- Most abundant in embryonic tissues and in

specialized connective tissues such as
synovial fluid, the lubricant of joints in the
body, and the vitreous humor of the eye where
it provides a clear, elastic gel that maintains
the retina in its proper position

Heparin
- Consists of alternating residues of D-
g l u c u ro n a t e - 2 - s u l f a t e a n d N - s u l f o - D -
glucosamine-6-sulfate

- Synthesized and stored in mast cells of various

tissues, particularly liver, lungs, gut

- Best known and undestood of its biological

functions is its anticoagulant activity

- Binds strongly the antithrombin III, a plasma

protein involved in terminating the clotting