Carbohydrates

Sources of Carbohydrates

Animal products Minor except milk (lactose)

Plants - major source Starch: storage of energy
Cellulose: structural

Photosynthesis
6CO2 + 6H2O + 673 Kcal C6H12O6 + 6O2

Nutrient Composition of an Adult Steer

Water 54% Fat 26% Protein 15% Ash 4.6% Carbohydrate <1%

little stored in the animal body

Carbohydrates (CHO)

C:H:O (1:2:1) The most abundant organic molecules in nature

Major component of plant tissue Comprise up to 70% or more of dry matter of forages Make up less than 1% of the weight of animals

Sources
Sugars, starch, cellulose, gums

Carbohydrates

Carbohydrates are polyhydroxy aldehydes or ketones

Aldehyde

Ketone

Classification

Classified according to the number of sugar molecules:

1. Monosaccharides - 1 unit 2. Disaccharides - 2 units 3. Oligosaccharides - 3 to 10 units 4. Polysaccharides - Greater than 10 units

Most plants contain different types of carbohydrates than animals

Monosaccharides (CnH2nOn)

Classified by the number of carbon atoms: 3-C triose 4-C tetrose nutritionally 5-C pentose important 6-C hexose

Sugars that contain four or more carbons exist primarily in cyclic form

Monosaccharides

Pentoses (5C)

Xylose and arabinose

Component in hemicellulose, glycoproteins Found in every living cell Found in compounds involved in metabolism:

Ribose

ATP/ADP Riboflavin DNA/RNA

Monosaccharides

Hexoses (6c)

Glucose

Component of starch, cellulose, and glycogen Major end-product of carbohydrate digestion in monogastrics Primary form of sugar used for energy

Glucose, fructose, and galactose are among the most important monosaccharides in living organisms

Monosaccharides

Hexoses (6c)

Fructose

75% of sugars in honey Found in fruits and cane sugar Component of milk sugar (lactose) May be metabolized to glucose
Found after hydrolysis of plant mannosans and gums; legumes

Galactose

Mannose

Disaccharides

Two monosaccharide molecules linked by a glycosidic (or acetal) bond

Lactose (galactose + glucose)

Milk sugar Found only in milk

Maltose (glucose + glucose)

Intermediate product of starch hydrolysis Found in starch from melting of barley Alpha 1-4 linkage fundamental for starch

Disaccharides

Sucrose (glucose + fructose)

Common table sugar Produced in leaves and stems of plants Found in sugar cane and sugar beets

Disaccharides

Cellulobiose (glucose + glucose)

Beta 1-4 linkage in cellulose Does not exist freely in nature

Oligo- and Poly-saccharides

Oligosaccharide

Chain of 310 sugar molecules Chain of 10+ sugar molecules

Polysaccharide

Polysaccharides

Heteropolysaccharide - composed of two or more types of monosaccharides

Homopolysaccharides - composed of one type of monosaccharide

Starch
basic unit: alpha-D glucose principal sugar form in cereals

Starch

Starch granules

Held together by H-bonds Insoluble in water

Raw starch is not well digested

Heat causes swelling of granules

Gelatinization Access for digestive enzymes Retrograded starch indigestible crystalline form after cooling

Starch

Three forms of starch:

1. Amylose

Apha 1-4 linkages Straight chain 14-30% of total plant starch Water soluble

Starch
2. Amylopectin Alpha 1-4 linkages with alpha 1-6 linkage at branch points 70-85% total plant starch Not water soluble

Starch
3. Glycogen Animal starch Small amounts in liver and muscle Highly branched Water soluble

Carbohydrates

General characteristics

the term carbohydrate is derived from the french: hydrate de carbone compounds composed of C, H, and O (CH2O)n when n = 5 then C5H10O5 not all carbohydrates have this empirical formula: deoxysugars, aminosugars carbohydrates are the most abundant compounds found in nature (cellulose: 100 billion tons annually)

General characteristics

Most carbohydrates are found naturally in bound form rather than as simple sugars

Polysaccharides (starch, cellulose, inulin, gums) Glycoproteins and proteoglycans (hormones, blood group substances, antibodies) Glycolipids (cerebrosides, gangliosides) Glycosides Mucopolysaccharides (hyaluronic acid) Nucleic acids

Functions

sources of energy intermediates in the biosynthesis of other basic biochemical entities (fats and proteins) associated with other entities such as glycosides, vitamins and antibiotics) form structural tissues in plants and in microorganisms (cellulose, lignin, murein) participate in biological transport, cell-cell recognition, activation of growth factors, modulation of the immune system

Classification of carbohydrates

Monosaccharides (monoses or glycoses)

Trioses, tetroses, pentoses, hexoses Di, tri, tetra, penta, up to 9 or 10 Most important are the disaccharides Homopolysaccharides Heteropolysaccharides Complex carbohydrates

Oligosaccharides

Polysaccharides or glycans

Carbohydrates (glycans) have the following

basic composition:
(CH2O)n

I or H - C - OH I

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 - polymers consisting of chains

Monosaccharides
Aldoses (e.g., glucose) have an aldehyde group at one end.
H C H HO H H C C C C OH H OH OH
HO H H

Ketoses (e.g., fructose) have a keto group, usually at C2.

CH2OH C C C C O H OH OH

CH2OH

CH2OH

D-glucose

D-fructose

D vs L Designation
D & L designations are based on the configuration about the single asymmetric C in glyceraldehyde. The lower representations are Fischer Projections.
CHO H C OH HO CHO C H

CH2OH

CH2OH

D-glyceraldehyde
CHO H C OH

L-glyceraldehyde
CHO HO C H

CH2OH

CH2OH

D-glyceraldehyde

L-glyceraldehyde

Sugar Nomenclature
For sugars with more than one chiral center, D or L refers to the asymmetric C farthest from the aldehyde or keto group.
O H O H

Most naturally occurring sugars are D isomers.

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

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.

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

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 Lsugars).

Hemiacetal & hemiketal formation

An aldehyde can react with an alcohol to form a hemiacetal.
H C R O H

R'

OH

R'

C R

OH

aldehyde
R

alcohol

hemiacetal
R

A ketone can react with an alcohol to form a hemiketal.

C R'

"R

OH

"R

C R'

OH

ketone

alcohol

hemiketal

Pentoses and H C OH 2 hexoses can HO C H D-glucose cyclize as the 3 H C OH (linear form) ketone or 4 aldehyde reacts H C OH 5 with a distal OH. CH2OH 6 Glucose forms an 6 CH2OH 6 CH2OH intra-molecular 5 5 O O H H H hemiacetal, as H H 4 1 4 H H OH OH the C1 aldehyde OH OH 2 & C5 OH react, OH 3 2 3 H OH H OH to form a 6-D-glucose -D-glucose member pyranose ring, named after of the cyclic sugars are called These representations pyran. projections. Haworth
1

CHO

OH
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

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.

6 CH 2OH

6 CH 2OH

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

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: (OH below the ring)

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

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.

Sugar derivatives
COOH
CH2OH H H H C C C OH OH OH

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

H HO H H

C C C C

OH H OH OH

CH2OH

D-ribitol

CH2OH

COOH

D-gluconic acid D-glucuronic acid

sugar alcohol - 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,

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 N-acetylglucosamine.

O H3C C NH

H O R H H OH H 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.

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 (methylglucopyranose).
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

Structural representation of sugars

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

Rules for drawing Haworth projections

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

O O

most aldohexoses are six-membered aldotetroses, aldopentoses, ketohexoses are 5-membered

Rules for drawing Haworth projections

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 drawing Haworth projections

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

Optical isomerism

A property exhibited by any compound whose mirror images are nonsuperimposable Asymmetric compounds rotate plane polarized light

POLARIMETRY
Measurement of optical activity in chiral or asymmetric molecules using plane polarized light Molecules may be chiral because of certain atoms or because of chiral axes or chiral planes

Measurement uses an instrument called a polarimeter (Lippich type) Rotation is either (+) dextrorotatory or (-) levorotatory

polarimetry
Magnitude of rotation depends upon:
1. the nature of the compound
2. the length of the tube (cell or sample container) usually expressed in decimeters (dm) 3. the wavelength of the light source employed; usually either sodium D line at 589.3 nm or mercury vapor lamp at 546.1 nm 4. temperature of sample

5. concentration of analyte in grams per 100 ml

[]

observed x 100 = lxc

D = Na D line T = temperature oC obs : observed rotation in degree (specify solvent) l = length of tube in decimeter c = concentration in grams/100ml [] = specific rotation

Specific rotation of various carbohydrates at 20oC

D-glucose D-fructose D-galactose L-arabinose D-mannose D-arabinose D-xylose Lactose Sucrose Maltose+ Invert sugar Dextrin

+52.7 -92.4 +80.2 +104.5 +14.2 -105.0 +18.8 +55.4 +66.5 +130.4 -19.8 +195

Disaccharides:
Maltose, a cleavage product of starch (e.g., amylose), is a disaccharide with an (1 4) glycosidic link between C1 - C4 OH of 2 glucoses. It is the anomer (C1 O points down).

6 CH2OH

6 CH2OH

H
4

O H
2 1

H
4

O H
2 1

H OH
3

H OH
3

OH

OH

H
6 CH 2OH

OH

maltose

OH

6 CH 2OH

H
4

O H
2 1

H O H
4

O H
2 1

OH

H OH
3

H OH
3

OH

OH

cellobiose

OH

Cellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer (O on C1 points up). The (1 4) glycosidic linkage is represented as a zigzag, but one glucose is actually flipped over relative

Other disaccharides include:

Sucrose, common table sugar, has a glycosidic bond linking the anomeric hydroxyls of glucose & fructose. Because the configuration at the anomeric C of glucose is (O points down from ring), the linkage is (12). The full name of sucrose is -D-glucopyranosyl(12)--D-fructopyranose.)

Lactose, milk sugar, is composed of galactose & glucose, with (14) linkage from the anomeric OH of galactose. Its full name is -D-

CH2OH H OH H OH O H OH H
1

H O

6CH OH 2 5 O 4 OH 3

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

CH2OH O H OH H H OH H O H

CH2OH O H OH H H OH OH H

H 1
2

OH

amylose

Polysaccharides:
Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch.
Glucose storage in polymeric form minimizes osmotic effects. Amylose is a glucose polymer with (14) linkages. It adopts a helical conformation.

The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the

CH 2OH H H OH OH H CH 2OH H OH H OH O H OH H H O H OH CH 2OH O H OH H H O H H O H

CH 2OH O H OH H H OH H 1 O 6 CH 2 5 H OH 3 H CH 2OH O H 2 OH 1 O H H O H 4 OH H H

amylopectin

CH 2OH H O OH H O H OH H H OH OH H

H O

H 4

OH

Amylopectin is a glucose polymer with mainly (14) linkages, but it also has branches formed by (16) linkages. Branches are generally longer than shown above. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can

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 O H H O H

CH2OH O H OH H 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

glycogen

CH2OH O H OH H H OH OH H

H O

H 4

OH

Glycogen, the glucose storage polymer in animals, is similar in structure to amylopectin. But glycogen has more (16) branches. 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 OH H OH O H OH H
1

H O H

6CH OH 2 5 O 4 OH 3

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

CH2OH O H OH H H H OH O H

CH2OH O H OH H H H OH OH

H 1
2

OH

cellulose

Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with (14) linkages. Every other glucose is flipped over, due to linkages.Waals interactions, van der that promotes intra-chain This cause cellulose chainsand inter-chain H-bonds to be and straight & rigid, and pack with a crystalline arrangement in thick bundles - microfibrils. Schematic of arrangement of cellulose chains in a microfibril. See: Botany online

CH2OH H OH H OH O H OH H
1

H O H

6CH OH 2 5 O 4 OH 3

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

CH2OH O H OH H H H OH O H

CH2OH O H OH H H H OH OH

H 1
2

OH

cellulose

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.