The Structure and Function of Macromolecules (Carbohydrates)

Important Point:

Polymers / Monomers
Many macromolecules consist of polymers A polymer is a large molecule built up from smaller building block molecules Monomers (a.k.a., subunits) are the building block molecules Small molecules common to all organisms are ordered into unique macromolecules . . . For each class (of compound) we will see that the macromolecules have emergent properties not found in their individual monomers.

Polymers, Monomers, and Lipids

polymer polysaccharide polypeptides polynucleic acids category of biomolecules monomer

carbohydrates monosaccharides
proteins RNA & DNA amino acids nucleotides

Chapter Carbohydrates
Carbohydrates
composition:

have

the

following

basic

(CH2O)n

I or H - C - OH I

the term carbohydrate is derived from the french: hydrate de carbone

Carbohydrates
Carbohydrates are The hydrates of carbon Carbohydrates often written as COH Basic chemical structure consists of sugar units Found as aldehydes or ketones derived from polyhydric alcohols A major source of energy from our diet. Composed of the elements C, H, and O. SARKARA (Sanskrit), SAKCHARON (Greek), SACCHARUM (Latin)
6

Carbohydrates
Carbohydrates Also called saccharides, which means sugars. often shown as aliphatic or linear structures, but exist in nature as ringed structures Are produced by photosynthesis in plants. Such as glucose are synthesized in plants from CO2, H2O, and energy from the sun. Are oxidized in living cells (respiration) to produce CO2, H2O, and energy.
7

What Do Carbohydrates Do?

Carbohydrates are important building blocks in the synthesis of other molecules. They indicate cell identity. (Glycocalyx on cells) They store chemical energy. (Glycogen and starch) They provide cells with fibrous structural materials. (Example: cellulose in plants) Intermediates in the biosynthesis of other basic biochemical entities (fats and proteins) Associated with other entities such as glycosides, vitamins and antibiotics) Participate in biological transport, cell-cell recognition, activation of growth factors, modulation 8 of the immune system

Types of Carbohydrates
The types of carbohydrates are (Usually by the number of sugar units in the molecule)
Monosaccharides - simple sugars with multiple OH groups. Based on number of carbons (3, 4, 5, 6), a monosaccharide is a triose, tetrose, pentose or hexose. Disaccharides - 2 monosaccharides covalently linked.

Oligosaccharides - a few monosaccharides covalently linked.

Polysaccharides (Glycans) - polymers monosaccharide or disaccharide units. consisting of chains of

Monosaccharides
Monosaccharides (simple sugars) cannot be broken down into simpler sugars under mild conditions, are consist of 3 to 6 carbon atoms, typically. A carbonyl group (aldehyde or ketone). Several hydroxyl groups. Aldoses and ketoses contain aldehyde and ketone functions, respectively. Triose, tetrose, etc. Denotes number of carbons. Aldoses with 3c or more and ketoses with 4c or more are chiral. Most (99%) are straight chain compounds D-glyceraldehyde is the simplest of the aldoses (aldotriose) All other sugars have the ending ose (glucose, galactose, ribose, lactose, etc)
10

Monosaccharides Vary in Structure

(1) Location of the carbonyl group. Aldose: The carbonyl is at the end of the monosaccharide. Ketose: The carbonyl is in the middle of the sugars carbon chain.
(2) Number of carbon atoms present. Triose: three Pentose: five Hexose: six (3) Spatial arrangement of their atoms. Different arrangement of the hydroxyl groups.

11

Monosaccharides Nomenclature
Functional group

Ketone
Number of carbons

Aldehyde Tetrulose Pentulose Hexulose Heptulose Octulose

12

4 5 6 7 8

Tetrose Pentose Hexose Heptose Octose

Aldoses
Aldoses are monosaccharides O With an aldehyde group at the end. CH aldose With many hydroxyl (OH) groups. H COH triose (3 C atoms) tetrose (4 C atoms) H COH pentose (5 C atoms) CH2OH hexose (6 C atoms) Erythose, an aldotetrose
13

Aldose sugars
H C (H C O OH)n H H C C O OH H H H C C C O OH OH H H H H C C C C O OH OH OH H H H H H C C C C C O OH OH OH OH

CH2OH Aldose

CH2OH Aldotriose n=1

CH2OH Aldotetrose n=2

CH2OH Aldopentose n=3

CH2OH Aldohexose n=4

Ketoses
Ketoses are monosaccharides CH2OH With a ketone group, C=O ketose usually at C2. With many hydroxyl (OH) H COH groups. triose (3 C atoms) tetrose (4 C atoms) pentose (5 C atoms) hexose (6 C atoms)
H COH HCOH CH2OH

Fructose, a ketohexose

16

Ketose sugars

CH2OH C (H C O OH)n

CH2OH C O H

CH2OH C C O OH H H

CH2OH C C C O OH OH H H H C CH2OH C C O OH OH OH

CH2OH

CH2OH Ketose Ketotriose n=0

CH2OH Ketotetrose n=1

CH2OH Ketopentose n=2

CH2OH Ketohexose n=3

Learning Check
Identify each as aldo- or keto- and as tetrose, pentose,

or hexose:
O C H H C OH H C OH H C OH H C OH CH2OH

CH2OH C O HO C H H C OH CH2OH

B
19

Solution
A. aldohexose B. ketopentose

20

Chapter Carbohydrates
Structures of Monosaccharides

Fisher projection: straight chain representation Haworth projection: simple ring in perspective Conformational representation: chair and configurations

boat
21

Some Monosaccharides

Note Basic Formula: (CH2O)n

Hence: Carbo (C) Hydrate (H2O)

Some Monosaccharides

All carbons in a monosaccharide are bonded to a hydroxyl group (-OH) except for one which is bonded to a carbonyl group (=O) (note that this statement is true only for the linear form of monosaccharides)

Chiral Carbons
A carbon is chiral if it has four different groups Chiral compounds have the same composition but are not superimposable Display in Fisher projection

CHO H OH CH2OH
D-glyceraldehyde
ENANTIOMERS

CHO HO H CH2OH
L-glyceraldehyde

Some Monosaccharides

The two simplest sugars

2 | 1C3 | 4

2 | 3C1 | 4

Note Numerous Chiral Carbons

Carbonyl Group Configurations

An aldose A ketose

Carbonyl group at end of carbon chain

Carbonyl group in middle of carbon chain

26

Fischer Projections
A Fischer projection Is used to represent carbohydrates. Places the most oxidized group at the top. Shows chiral carbons as the intersection of vertical and horizontal lines.

27

D and L Notations
D & L designations are based on the configuration about the single asymmetric C in glyceraldehyde. For sugars with more than one chiral center, in a Fischer projection, the OH group on the Chiral carbon farthest from the carbonyl group determines an L or D isomer. Left is assigned the letter L for the L-isomer. Right is assigned the letter D for the D-isomer.

28

D and L Notations
D & L sugars are mirror images of one another. They have the same name, e.g., D-glucose & L-glucose. Other stereoisomers have unique names, e.g., glucose, mannose, galactose, etc. Vant Hoffs Rule: The number of stereoisomers is 2n, where n is the number of asymmetric centers. The 6-C aldoses have 4 asymmetric centers. Thus there are 16 stereoisomers (8 D-sugars and 8 L-sugars).
O H O H C H C OH HO C H H C OH H C OH CH2OH
D-glucose

C HO C H H C OH HO C H HO C H CH2OH
L-glucose

29

Examples of D and L Isomers of Monosaccharides

O C H H HO H H
D-glucose

O C H O C H H OH H OH H OH CH2OH
D-ribose

OH H OH OH CH2OH

HO H H HO

H OH OH H CH2OH

L-galactose

30

Learning Check
Identify each as the D or L isomer. A. B.
O C H HO HO HO H H H CH2OH H HO O C H OH H CH2OH HO H H

C.
CH2OH O H OH OH CH2OH

__-ribose

__- threose

__- fructose
31

Solution
Identify each as the D or L isomer. A. B.
O C H HO HO HO H H H CH2OH H HO O C H OH H CH2OH HO H H

C.
CH2OH O H OH OH CH2OH

L-ribose

L-threose

D-fructose
32

More Stereochemistry
Know these definitions Stereoisomers that are mirror images of each other are enantiomers. Pairs of isomers that have opposite configurations at one or more chiral centers but are NOT mirror images are diastereomers. Two sugars that differ in configuration at only one chiral center are epimers.

D-mannose and D-glucose are C-2 epimers.

D-galactose and D-glucosea re C-4 epimers
33

Epimers

CHO H H H OH OH OH CH 2OH HO H H

CHO H OH OH CH 2OH
HO H H H

CHO OH H OH OH CH 2OH HO HO H H

CHO H H OH OH CH 2OH H HO HO H

CHO OH H H OH CH 2OH

D-ribose C-2 epimers

D-arabinose

D-glucose

D-mannose

D-galactose

34

Varying Configurations of Hydroxyl Groups

Glucose Galactose

Different configuration of hydroxyl groups

35

D-Glucose (Dextrose) Blood Sugar

D-glucose is Most common carbohydrate Found in fruits, corn syrup, and honey. An aldohexose with the formula C6H12O6. Rotate the polarized light to the right. The monosaccharide in polymers of starch, cellulose, and glycogen.

36

D-Fructose (Levulose) Fruit Sugar

D-fructose Is a ketohexose C6H12O6. Rotate polarized light to the left. Is the sweetest carbohydrate. Is found in fruit juices and honey. Converts glucose body. in to the
CH2OH C O HO C H H C OH H C OH CH2OH D-Fructose
37

D-Galactose
D-galactose is
O C H H C OH HO C H HO C H H C OH CH2OH D-Galactose

An aldohexose C6H12O6. Not found free in nature. Obtained from lactose, a disaccharide. A similar structure to glucose except for the OH on C4.

38

Learning Check
Draw the structure and Fischer projection of D-fructose.

39

Solution
CH2OH C O HO C H H C OH H C OH CH2OH D-Fructose
H H OH OH CH2OH Fischer projection HO CH2OH C=O H

40

Chapter Carbohydrates
Cyclic Structures of Monosaccharides
CH2OH O OH OH

OH

OH

PYRAN

FURAN

41

Hemiacetal & hemiketal formation

An aldehyde can react with an alcohol to form a hemiacetal. A ketone can react with an alcohol to form a hemiketal. Cyclic form of glucose is mainly a pyranose. Cyclic form of fructose is mainly a furanose.
H C R O H

R'

OH

R'

C R

OH

aldehyde
R C R' O

alcohol

hemiacetal
R

"R

OH

"R

C R'

OH

ketone

alcohol

hemiketal

Anomeric Carbon --- The carbon atom which is involved in hemiacetal or acetal formation.

Cyclic Structures
Pentoses and hexoses can cyclize as the ketone or aldehyde reacts with a distal OH. Glucose forms an intramolecular hemiacetal, as the C1 aldehyde & C5 OH react, to form a 6member pyranose ring, named after pyran.
1

CHO C C C C OH H

H HO H H

2 3 4 5 6

D-glucose

OH (linear form) OH

CH2OH
6 CH2OH

6 CH2OH

H
4

O H
2

H
1

H
4

O H
2

OH
1

H OH
3

H OH
3

OH

OH

OH

OH

OH

-D-glucose

-D-glucose

These representations of the cyclic sugars are called Haworth projections.

Cyclic Structures
Fructose forms either a 6-member pyranose ring, by reaction of the C2 keto group with the OH on C6, or a 5-member furanose ring, by reaction of the C2 keto group with the OH on C5.
1

CH2OH O H OH OH HOH2C 6
5

2C

HO H H

C C C

O H HO
3

1 CH2OH 2

4 5 6

CH2OH

OH

OH

D-fructose (linear)

-D-fructofuranose

Anomers
Anomers are two sugars that differ in configuration only at the C that was the carbonyl carbon in the open chain form. Ano gr: for upper Anomers like epimers are a kind of diastereomers.

45

Cyclic Structures
Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers are called anomers, & . Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1: For D-sugars, has OH down, has OH up. For L-sugars, the reverse is true.
6 CH 2OH 6 CH 2OH 5 4

O H
2

H
1

H
4

O H
2

OH
1

H OH
3

H OH
3

OH

OH

OH

OH

OH

-D-glucose

-D-glucose

Optical Isomerism
A property exhibited by any compound whose mirror images are non-superimposable Asymmetric compounds rotate plane polarized light Enantiomers - Optical isomers rotate the beam of plane-polarized light for the same angle, but in opposite direction Rotation is either (+) dextrorotatory or (-) levorotatory Equimolar mixture of optical isomers has no optical activity - racemic mixture Measurement of optical activity in chiral or asymmetric molecules using plane polarized light Molecules may be chiral because of certain atoms 48or because of chiral axes or chiral planes

Mutarotation
Process by which various anomeric forms attain an equilibrium in solution Change in optical activity of a optically active compound in solution.

The optical rotation of glucose solution could change with time. It involves interconversion of - and -D-glucose.
[]D20 = 112.2 for -D-glucose []D20 = 18.7 for -D-glucose - D - glucose -> D glucose <- - D glucose 20D = 113 20D = 52 20D = 19
49

At equilibrium = 35% of - form and 65% of - form.

Mutarotation

~37%
<<1%

0.0026%

~63%
50

Cyclic Structures
Because of the tetrahedral nature of carbon bonds, pyranose sugars actually assume a "chair" or "boat" configuration, depending on the sugar. The representation above reflects the chair configuration of the glucopyranose ring more accurately than the Haworth projection.
H OH
4 6 5 3

H OH H O H
2

H O HO H HO H H OH OH H

HO HO H

OH 1 OH

-D-glucopyranose

-D-glucopyranose

Cyclic Structures
Cyclic structures Are the prevalent form of monosaccharides with 5 or 6 carbon atoms.
O O

Form when the hydroxyl group on C-5 reacts with the aldehyde group or ketone group.

52

Cyclic Haworth Structures

Stable cyclic hemiacetals form When the C=O group and the OH are part of the same molecule. For hexoses, the hydroxyl group on C-5 reacts with the aldehyde group or ketone group. The cyclic structure of a D-isomer has the last CH2OH group located above the ring.

CH2OH O

53

Rules for projections

drawing

Haworth

Draw either a six or 5-membered ring including oxygen as one atom

O O

Most aldohexoses are six-membered Aldotetroses, aldopentoses, ketohexoses are 5membered

Rules for projections

drawing

Haworth

Next number the ring clockwise starting next to the oxygen

5 4 3 2 O 1 4 3 2 O 1

If the substituent is to the right in the fisher projection, it will be drawn down in the haworth projection (down-right rule)

Rules for projections

drawing

Haworth

For D-sugars the highest numbered carbon (furthest from the carbonyl) is drawn up. For L-sugars, it is drawn down For D-sugars, the OH group at the anomeric position is drawn down for and up for . For L-sugars is up and is down

Drawing the Cyclic Structure for Glucose

STEP 1 Number the carbon chain and turn clockwise to form a linear open chain. H O

C
1

H C OH
2

H
6 5

H OH H
4 3 2 1

HO 3 C H H 4 C OH H 5 C OH
6 CH2OH

O H

HOCH2 C C C C C OH OH H OH

57

Cyclic Structure for Glucose

STEP 2 Bend the chain to make a hexagon Bond the C5 O to C1. Place the C6 group above the ring. Write the OH groups on C2 and C4 below the ring. Write the OH group on C3 above the ring. Write a new OH on C1.

CH2OH
6 5 4

O
1

OH

OH
3

OH OH

58

Cyclic Structure for Glucose (cont)

STEP 3 The new OH on C1 is drawn Down for the anomer. Up for the anomer.
CH2OH CH2OH

O
OH OH OH OH

OH

O OH

OH OH

-D-glucose

-D-glucose
59

Summary of the Formation of Cyclic Glucose

These are all Glucose

Memorize this structure

60

Linear and Ring Forms

Linear form of glucose Ring forms of glucose
Oxygen from the 5-carbon bonds to the 1-carbon, resulting in a ring structure

-Glucose

-Glucose

61

-D-Glucose and -D-Glucose in Solution

When placed in solution, Cyclic structures open and close. -D-glucose converts to -D-glucose and back. There is only a small amount of open chain.
CH2OH O OH OH

CH2OH O OH
OH

H O C H

CH2OH O OH OH

OH

OH OH

OH

-D-glucose (36%)

D-glucose (open) (trace)

OH -D-glucose (64%)
62

Cyclic Structure of Fructose

Fructose Is a ketohexose. Forms a cyclic structure. Reacts the OH on C-5 with the C=O on C-2.
CH2OH C O HO C H H C OH H C OH CH2OH OH CH2OH O OH OH OH CH2OH CH2OH O OH OH CH2OH

D-fructose

-D-fructose

-D-fructose
63

Learning Check
Write the cyclic form of -D-galactose

O C H H C OH HO C H HO C H H C OH CH2OH
64

Solution

CH2OH OH OH OH O

OH

-D-galactose
65

Saccharides Isomerism - Review

STRUCTURE isomerism (constitutional) same summary formula, different functional groups aldose ketose glucose fructose OPTICAL isomerism (antipods, enantiomers) D- and L- isomerism mirror images D-glucose L-glucose EPIMERISM different orientation of hydroxyl on one C ( not reference) glucose manose glucose galactose PYRANOSE-FURANOSE-ACYKLIC FORM -D-glucopyranose -D-glucofuranose acyclic glucose ANOMERISM -D-glucopyranose -D-glucopyranose mutarotation

Chapter Carbohydrates
Chemical Properties of Monosaccharides

67

Reducing Sugars
Are monosaccharides with a carbonyl group that oxidizes to give a carboxylic acid. Sugars with free anomeric carbons Undergo reaction with benedicts reagent (cu2+) to give the corresponding carboxylic acid. Fehlings reagent: CuSO4 (blue) + RC(=O)H Cu2O (red) + RCO2 Tollens reagent: Ag+ Ag0 Include the monosaccharides glucose, galactose, and fructose.
68

Oxidation of D-Glucose
O C H
Benedicts reagent

O C OH H C OH
[O]

Glucose is oxidized to a carboxylic acid

H C OH HO C H H C OH H C OH CH2OH D-glucose

+ Cu

2+

HO C H H C OH H C OH CH2OH D-gluconic acid

+ Cu2O(s)

Cu+ (reduced form)

Glucose is a reducing sugar

69

Reduction of Monosaccharides
The reduction of monosaccharides Involves the carbonyl group. Produces sugar alcohols called alditols. Such as D-glucose gives D-glucitol also called sorbitol.
D-Glucitol

70

Learning Check
Write the products of the oxidation and reduction of D-mannose.
O C H HO HO H H H H OH OH CH2OH
D-mannose
71

Solution
Write the products of the oxidation and reduction of D-mannose.
O CH2OH HO HO H H H H OH OH CH2OH
D-mannitol

O C OH Oxidation HO HO H H H H OH OH CH2OH
D-mannonic acid
72

C H Reduction HO HO H H H H OH OH CH2OH
D-mannose

Chapter Carbohydrates
Sugar Derivatives

73

Sugar derivatives
COOH
CH2OH H H H C C C OH

CHO H HO H H C C C C OH H OH OH

H HO

C C C C

OH H OH OH

OH

H
OH

H
CH2OH

D-ribitol

CH2OH

COOH

D-gluconic acid D-glucuronic acid

sugar alcohol (alditols) - lacks an aldehyde or ketone; e.g., ribitol. sugar acid - the aldehyde at C1, or OH at C6, is oxidized to a carboxylic acid; e.g., gluconic acid, glucuronic acid.

Sugar derivatives
CH2OH H H OH OH H NH2 O H OH OH H N H H H H OH CH2OH O H O OH C CH3 H

-D-glucosamine

-D-N-acetylglucosamine

amino sugar - an amino group substitutes for a hydroxyl. An example is glucosamine. The amino group may be acetylated, as in Nacetylglucosamine.

Sugar derivatives
O H3C C NH R H H OH H H O H OH COO HC R= HC OH OH

CH2OH

N-acetylneuraminate (sialic acid)

N-acetylneuraminate (N-acetylneuraminic acid, also called sialic acid) is often found as a terminal residue of oligosaccharide chains of glycoproteins. Sialic acid imparts negative charge to glycoproteins, because its carboxyl group tends to dissociate a proton at physiological pH, as shown here.

Sugar derivatives
Deoxy sugars: These are monosaccharides which lack one or more hydroxyl groups on the molecule; example: 2-deoxy ribose - constituents of DNA, 6deoxy-L-mannose (L-rhamnose) is used as a fermentative reagent in bacteriology, etc. Sugar esters: phosphate esters like ATP are important. Acetals, ketals and glycosides: basis for oligo- and poly-saccharides.

77

Chapter Carbohydrates
Glycosidic Bonds

78

Glycosidic Bonds
The anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together, splitting out water to form a glycosidic bond: R-OH + HO-R' R-O-R' + H2O E.g., methanol reacts with the anomeric OH on glucose to form methyl glucoside (methyl-glucopyranose).
H OH H O HO HO H H H OH OH H H2O H OH H O HO HO H H OH OCH3

CH3-OH

-D-glucopyranose

methanol

methyl--D-glucopyranose

Glycosidic Bonds
with hemiacetal hydroxyl of other saccharide

nonreducing disaccharides
with other then hemiacetal hydroxyl of other saccharide

reducing disaccharides
with nonsugar hydroxyl (alcohol, sterol, heterocycle)

O-glycosides
with amino(imino) group

N-glycosides
80

Glycosidic Bonds
When an anomeric carbon participates in a glycosidic bond, it cannot be oxidized by ferric or cupric ion.
The sugar containing that anomeric carbon cannot exist in linear form and can no longer act as a reducing sugar. reducing end: the end of a chain with a free anomeric carbon

81

Chapter Carbohydrates
Disaccharides

82

Important Disaccharides
A disaccharide Consists of two monosaccharides. 2 sugars joined by a condensation reaction to form a glycosidic bond Monosaccharides Disaccharide Glucose + glucose maltose + H2O Glucose + galactose lactose + H2O Glucose + fructose sucrose + H2O

83

Maltose (Malt Sugar)

Maltose is Composed of two D-glucose molecules. Obtained from the hydrolysis of starch. Linked by an -1,4-glycosidic bond formed from the OH on C1 of the first glucose and OH on C4 of the second glucose. Used in cereals, candies, and brewing. Found in both the - and - forms. Reducing sugar Shows mutarotation Its full name is -D-glucopyranosyl-(14)--D84 glucopyranose

Formation of Maltose

Reducing end

85

Cellobiose
Cellobiose is A disaccharide Composed of two D-glucose molecules. Obtained from the hydrolysis of cellulose. Linked by an -1,4-glycosidic bond formed from the OH on C1 of the first glucose and OH on C4 of the second glucose. The -1,4-glycosidic linkage is represented as a zig-zag, but one glucose is actually flipped over relative to the other. Reducing sugar Shows mutarotation Its full name is -D-glucopyranosyl-(14)--D86 glucopyranose

Formation Of Cellobiose

6 CH 2OH

6 CH 2OH

H
4

O H
2 1

H O H
4

O H
2 1

OH

H OH
3

H OH
3

Reducing end
H

OH

OH

cellobiose

OH

Lactose (Milk Sugar)

Lactose Is a disaccharide of -d-galactose and - or -dglucose. Contains a -1,4-glycosidic bond. Is found in milk and milk products. Reducing sugar Shows mutarotation Its full name is b-d-galactopyranosyl-(14)-a-dglucopyranose Used in infant formulations, medium for penicillin production and as a diluent in pharmaceuticals
88

Formation of Lactose

Reducing end

Sucrose (Table Sugar)

Is obtained from sugar cane and sugar beets. Consists of -d-glucose and -d-fructose.. Has an ,-1,2-glycosidic bond. Non-reducing sugar Do not show mutarotation The full name of sucrose is a-d-glucopyranosyl(12)-b-d-fructopyranose. Invert sugar --- when sucrose in solution, the rotation changes from detrorotatory (+66.5) to levorotatory (19.8). So, sucrose is called invert sugar. Used pharmaceutically to make syrups, troches
90

Formation of Sucrose

Formation of Sucrose
Note that Fru has been flipped and that it is in the -position

92

Trehalose
Trehalose is a disaccharide that occurs naturally in insects, plants, fungi, and bacteria. The major dietary source is mushrooms. Trehalose is used in bakery goods, beverages, confectionery, fruit jam, breakfast cereals, rice, and noodles as a texturizer, stabilizer, humectant, or formulation aid with a low sweetening intensity
CH2OH H O OH H HO H OH O HH H OH H OH H HOH2C O H

OH
93

TREHALOSE

Learning Check
Write the structures and names of the two monosaccharides that form when sucrose is hydrolyzed.

94

Solution

-D-glucose

-D-fructose
95

Learning Check
Identify the monosaccharides in each of the following: A. lactose (1) -D-glucose (2) -D-fructose (3) -D-galactose

B. maltose (1) -D-glucose (2) -D-fructose C. sucrose (1) -D-glucose (2) -D-fructose

(3) -D-galactose

(3) -D-galactose
96

Solution
Identify the monosaccharides in each of the following: A. lactose (1) -D-glucose (3) -D-galactose B. maltose (1) -D-glucose C. sucrose (1) -D-glucose

(2) -D-fructose

97

Chapter Carbohydrates

Oligosaccharides

99

Raffinose
(Galactose + Glucose + Fructose)

6-0--D-Galactopyranosyl (1->6)-2-0--DGlucopyranosyl (1->2)--D-Fructofuranoside

CH2 OH OH OH OH O O OH OH OH O OH CH2 O CH2 OH O HO CH2 OH

Melbiose

Sucrose Moiety
100

Stachyose
(Galactose + Galactose + Glucose + Fructose)

6-0-a-D-Galactopyranosyl (1->6)-6-0-a-DGalactopyranosyl (1-> 6) -2-0-a-D-Glucopyranosyl-bD-Fructofuranoside

Flatulence Factor
CH 2 OH OH OH OH O O OH OH OH CH2 O O OH OH OH O OH CH2 O CH2OH O HO CH2OH
101

Chapter Carbohydrates

Polysaccharides

102

Polysaccharides
Polysaccharides

Polysaccharides are polymers that form from monosaccharides through a condensation reaction between two hydroxyl groups to create a glycosidic linkage.
(1) The monomers joined by glycosidic linkages can be identical or different. (2) The glycosidic linkages can form between any two hydroxyl groups; so the location and geometry of these bonds vary widely. 103

Polysaccharides
characteristics:

polymers (MW from 200,000) White and amorphous products (glassy) not sweet not reducing; do not give the typical aldose or ketose reactions) form colloidal solutions or suspensions

104

Polysaccharides
Functions: storage, structure, recognition Nomenclature: homopolysaccharide vs. heteropolysaccharide. Lower the osmotic pressure. Starch and glycogen are energy storage molecules. Chitin and cellulose are structural molecules. Cell surface polysaccharides are recognition molecules.

105

Starch
Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch. Most starch amylopectin. is 10-30% amylose and 70-90%

Glucose storage in polymeric form minimizes osmotic effects. The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the reducing end.

Starch is used as an excipient, a binder in medications to aid the formation of tablets. Industrially it has many applications such as in adhesives, paper making, biofuel, textiles. 106

Structures of Amylopectin

Amylose

and

107

Amylose
Amylose is A polymer of -d-glucose molecules. Linked by -1,4 glycosidic bonds. A continuous (unbranched) chain. 200 to 20 000 glucose units helix
108

Amylopectin
Amylopectin Is a polymer of -D-glucose molecules. Is a branched-chain polysaccharide. Has -1,4-glycosidic bonds between the glucose units. Has -1,6 bonds to branches in every 12-30 residues. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can occur.

109

Starch
Amylose and amylopectin are poorly soluble in water, but form micellar suspensions. In these suspensions, amylose is helical and iodine fits into the helices to produce a blue color. Amylopectin produces a red-violet color with I2. Branches provide a mechanism for quickly releasing (or storing) glucose units for (or from) metabolism.

110

Glycogen
Glycogen Is the polysaccharide that stores -Dglucose in muscle, the glucose storage polymer in animals. Is similar to amylopectin, but is more highly branched. Glycogen constitutes up to 10% of liver mass and 1-2% of muscle mass. Glycogen is stored energy for the organism. (1,6) branches every 8-12 residues . Like amylopectin, glycogen gives a redviolet color with iodine.

111

Glycogen
The highly branched structure permits rapid glucose release from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants.
CH2OH H H OH OH H CH2OH H OH H OH O H OH H H O H OH CH2OH O H OH H H OH H O H 4 O H H O H H OH H CH2OH O H OH H 1 O 6 CH2 5 H OH 3 H CH2OH O H 2 OH 1 O H H O H 4 OH H H O OH H H CH2OH O H OH H H OH OH
112

glycogen

carbon and energy (glucose) storage molecules

more branching

Dextrans
A small but significant difference from starch and glycogen. If you change the main linkages between glucose from (1,4) to (1,6), you get a new family of polysaccharides dextrans. Branches can be (1,2), (1,3), or (1,4). Dextrans formed by bacteria are components of dental plaque. Cross-linked dextrans are used as "Sephadex" gels in column chromatography. used as plasma extenders (treatment of shock) 114 These gels are up to 98% water!

Structural Polysaccharides
Composition similar to storage polysaccharides, but small structural differences greatly influence properties. Cellulose is the most abundant natural polymer on earth. Cellulose is the principal strength and support of trees and plants . Cellulose can also be soft and fuzzy - in cotton.

115

Other Structural Polysaccharides

Chitin - exoskeletons of crustaceans, insects and spiders, and cell walls of fungi. similar to cellulose, but C-2s are N-acetyl cellulose strands are parallel, chitins can be parallel or antiparallel. Alginates Ca2+-binding polymers in algae. Agarose and agaropectin - galactose polymers Glycosaminoglycans - repeating disaccharides with amino sugars and negative charges.

116

Cellulose
Cellulose Is a polysaccharide of glucose units in unbranched chains. Has -1,4-glycosidic bonds. Cannot be digested by humans because humans cannot break down -1,4-glycosidic bonds.

117

Cellulose
Gives no color with iodine. A structural polysaccharide Yields glucose upon complete hydrolysis Partial hydrolysis yields cellobiose

118

Cellulose
Every other glucose is flipped over, due to linkages. This promotes intra-chain and inter-chain H-bonds and van der Waals interactions, that cause cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles microfibrils. Multisubunit Cellulose Synthase complexes in the plasma membrane spin out from the cell surface microfibrils consisting of 36 parallel, interacting cellulose chains. These microfibrils are very strong. The role of cellulose is to impart strength and rigidity to plant cell walls, which can withstand high hydrostatic pressure gradients. Osmotic swelling is prevented.

119

Schematic of arrangement of cellulose chains in a microfibril.

Cellulose

Know the difference

Cellulose
Cellulose is a Structural polysaccharide

Most organisms cannot digest (hydrolyze) cellulose

Cellulose

Organisms that can digest cellulose include the microorganisms living the gastrointestinal tract of many organisms typified especially by cows and termites and many fungi (i.e., the things that eat the wood of fallen trees)

Chitin
Chitin is the second most abundant carbohydrate polymer Like cellulose, chitin is a structural polymer Present in the cell wall of fungi and in the exoskeletons of crustaceans, insects and spiders Chitin is used commercially in coatings (extends the shelf life of fruits and meats) A chitin derivative binds to iron atoms in meat and slows the rancidity process

123

Chitin

124

Learning Check
Identify the polysaccharides and types of glycosidic bonds in each of the following:

A.

B.

C.

125

Solution
A. Cellulose
B. Amylose Amylopectin C. Glycogen

-1,4-glycosidic bonds
-1,4-glycosidic bonds -1,4-and -1,6-glycosidic bonds -1,4-and -1,6-glycosidic bonds (more branched than amylopectin)

126

Polysaccharides: Unbranched

Branched

and

127

Polysaccharides: Unbranched

Branched

and

128

Polysaccharides: Unbranched

Branched

and

Polysaccharides: Unbranched

Branched

and

Mucopolysaccharides (Glycosaminoglycans)
Glycosaminoglycans (mucopolysaccharides) are linear polymers of repeating disaccharides. The constituent monosaccharides tend to be modified, with acidic groups, amino groups, sulfated hydroxyl and amino groups, etc. Glycosaminoglycans tend to be negatively charged, because of the prevalence of acidic groups.

131

Hyaluronate
Hyaluronate (hyaluronan) is a glycosaminoglycan with a repeating disaccharide consisting of 2 glucose derivatives, glucuronate (glucuronic acid) & N-acetylglucosamine. The glycosidic linkages are b(13) & b(14).
D-glucuronate
6COO

CH2OH
5

H O H
2 1 4

O H
1 O

H
4

H OH
3

OH O

NHCOCH3

OH

N-acetyl-D-glucosamine
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hyaluronate

Heparan Sulfate
Heparan sulfate is initially synthesized on a membrane-embedded core protein as a polymer of alternating N-acetylglucosamine and glucuronate residues. Later, in segments of the polymer, glucuronate residues may be converted to the sulfated sugar iduronic acid, while N-acetylglucosamine residues may be deacetylated and/or sulfated.
iduronate-2-sulfate
H H COO OH

N-sulfo-glucosamine-6-sulfate
CH2OSO3 H O H H OH O H O H NHSO3
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O H

OSO3

heparin or heparan sulfate - examples of residues

Heparin
Heparin, a soluble glycosaminoglycan found in granules of mast cells, has a structure similar to that of heparan sulfates, but is more highly sulfated. When released into the blood, it inhibits clot formation by interacting with the protein antithrombin. Heparin has an extended helical conformation.

134

Some More GAGs

135

136

Importance of carbohydrates
We use them as our major energy source (4 kcal/g)
Humans : starch, sucrose and fructose 80% of our energy intake (average)

We use them for their sweet taste We use them to provide structure and texture in food products
Bread & pudding (starch); Dextrin (soft drinks); Pectin (jellies)

We use them to lower water activity of food products and also influence ice crystallization
Intermediate moist foods; Ice cream

Importance of carbohydrates
We use them as fat substitutes
Modifies starches & celluloses, and gums

We use them to impart desirable flavors and colors for certain food products
Maillard browning

We use them as an energy source in fermentation reactions

Yogurt

We use them for their reported health benefits

Dietary fiber