Carbohydrates

Structure & Function of Biomolecules

Carbohydrates

Most abundant biomolecule Many functions

Energy/energy storage Structural elements Mediator of interactions

Monosaccharides

Simple sugars Polyhydroxy aldehydes or ketones

Monosaccharides

General formula: (CH2O)n

n=3-7

Most highly oxidized carbon at top (C1)

Important Monosaccharides
H OH H HO HO H H OH H OH
OH OH

HO
O

O HO OH
H HO H

O OH OH H

HO

OH

Glucose

Fructose

Galactose

Must be able to draw Fischer projections and Haworth projections of these.

Stereoisomers
H

vant Hoffs rule

# of stereoisomers = where n = # of assymmetric carbons.

2n
H HO H H

C C C C C

O OH H OH OH

n=4 # stereoisomers = 16

CH2OH

Types of Stereoisomers

Enantiomers

Mirror images

Diastereomers
Not mirror images

Epimers

Differ at a single chiral carbon

Examples
H C H HO H H C C C C O OH H OH OH HO H HO HO H C C C C C O H OH H H
H H H H H C C C C C O OH OH OH OH
HO HO HO H H C C C C C O H H H OH

CH2OH

CH2OH

CH2OH

CH2OH

D-glucose

L-glucose (enantiomer)

D-allose (epimer at C3)

D-talose (diastereomer)

Configuration

Look at chiral carbon farthest from carbonyl carbon to determine D or L configuration.

H C H HO H C C C C O OH H OH OH HO H HO HO H C C C C C O H OH H H

OH on right, then D configuration

OH on left, then L configuration

CH2OH

CH2OH

D-glucose

L-glucose

Reactions with Alcohols

Cyclization
H H HO H H C C C C C O OH H OH OH
H H HO H H C C C C C CH2OH OH OH

O
H OH

CH2OH

Furanoses/Pyranoses
O O

Furan

Pyran

Haworth Projections
Anomers

Mutarotation

a and b forms spontaneously interconvert in an aqueous environment. Proportion of each anomer differs for each sugar.

Reducing Sugars

Sugars that are susceptible to oxidation.

(reducing)

Look at C1 on aldoses or C2 on ketoses. If a free OH is present, then the sugar is a reducing sugar.
(not reducing)

Oxidation Reactions
Oxidation of aldehyde = aldonic acid
OH
C O OH H OH OH O
H HO H H C C C C C C OH O OH H OH OH O

Oxidation of terminal CH2OH = uronic acid

H

Oxidation of both = aldaric acid

OH

C H HO H H C C C C

O
H C C C C C

OH
HO

H
H

OH
H

OH

CH2OH
OH

D-Gluconic acid

D-Glucuronic acid

D-Glucaric acid

Reduction Reactions
OH CH2OH C H HO H H C C C C O H OH C C C C OH H OH OH

H2
H OH OH

HO H H

Catalyst

CH2OH CH2OH

D-Glucose

D-Glucitol (Sorbitol) Sugar alcohol

Isomerization

Generally enzyme catalyzed reactions. Important in carbohydrate metabolism.

Modifications of Monosaccharides
O-O

P H O

CH2OH
H O OH H OH H

OH O

HO HO

OH

N-acetyl-a-D-glucosamine

b-D-Glucose-6-phosphate

2-deoxy-b-D-ribose

Glycosidic Linkages

Glycosidic Linkages
Glycosidic linkage

Aglycone

Disaccharides

Bond type

Look at first subunit to determine if a or b Number according to 1st subunit then 2nd subunit
CH2OH

a 1-4 linkage
O

CH2OH O OH

OH OH OH O

OH

OH

Maltose (a-D glucose (a 1-4) b-D glucose)

Sucrose (must be able to draw)

Table sugar

Is sucrose a reducing sugar?

No, because glycosidic linkage joins the 2 anomeric carbons.

a-D glucose (a 1-2) b-D fructose

Oligosaccharides

3 - 10 or more subunits Often attached to proteins or lipids to form glycoproteins or glycolipids, respectively. N-linked

Attached via asparagine.

O-linked

Attached via threonine or serine or OH on lipid

Polysaccharides

Composed of many subunits. Homopolysaccharides or heteropolysaccharides

Storage Polysaccharides: Plants

Starch

Glucose monomers

Two forms

Amylose

Unbranched a1-4 linkages

Amylopectin

a1-4 backbone with a1-6 branches.

Branches occur ~12-25 residues & contain ~20-25 glucoses

Use a amylase to digest.

Storage Polysaccharides: Animals

Glycogen

Stored in liver & in muscles. a1-4 backbone with a1-6 branches. Branches occur ~10 residues & contain ~ 812 glucoses. Glycogen phosphorylase breaks a1-4 linkages. Debranching enzyme breaks a1-6 linkages.

Framework of Nucleic Acids

Deoxyribose (DNA)

Ribose (RNA)

Structural Elements: Plants

Cellulose Homopolysaccharide

Glucose subunits joined by b1-4 linkages.

Found in plant cell wall. Mammals lack cellulose degrading enzyme.

Structural Elements: Arthropods and Some Fungi

Chitin Homopolysaccharide

N-acetylglucosamine monomers joined by b1-4 linkages.

Makes up exoskeleton of arthropods and cell wall of some fungi

Structural Elements: Animals

Glycosaminoglycans (GAGs)

Heteropolysaccharides

Disaccharide repeating units

Negatively charged at physiological pH.

Bind a lot of H2O.

Cell-Cell Recognition: Blood Group Antigens

Carbohydrate portion of blood group glycolipids

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