Chapter 11: Carbohydrates: Structure and Biological Function

MARIA CRISTINA R. RAMOS, Ph.D. Professor , Department of Chemistry

Selaginella lepidophylla- a desert plant which can

adapt to dehydrating condition by synthesizing trehalose, and can resume normal metabolism when water is available-hence its nickname is resurrection plant.

Roles of Carbohydrates
Storage of metabolic fuel Structural framework of nucleic acids Structural elements in the cell walls of bacteria and plants Linked to proteins and lipids which are involved in cell recognition

Monosaccharides are classified by their number of carbon atoms

Name Triose Tetrose Pentose Hexose Heptose Octose Formula C3 H6 O3 C4 H8 O4 C5 H1 0 O 5 C6 H1 2 O 6 C7 H1 4 O 7 C8 H1 6 O 8

Monosaccharides Stereoisomers

Carbohydrates contain many chiral carbons

OPTICAL ISOMERS
Stereosiomers can be distinguished using plane of polarized light

Naming stereoisomers

Based on the structure of L- and D-glyceraldehyde

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- sugars are the most common carbohydrates. D-refers to the right hand orientation of the OH on the chiral carbon farthest from the carbonyl carbon L-sugars: L refers to the left hand orientation of the OH on the chiral carbon farthest from the carbonyl carbon

EXERCISE
Draw the possible structure(s) of 1. aldotetrose 2. ketotetrose

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

The most common sugar Known as dextrose Also known as blood sugar

CH2OH

D-glucose

Galactose
One of the monosaccharides in the disaccharide lactose Found in plant gums and pectins polysaccharides An epimer of glucose at C4 Converted to glucose during metabolism

Fructose
One monosaccharide in the disaccharide sucrose (table sugar). Called levulose or fruit sugar Found in honey and fruits Sweeter than sucrose and glucose Commercially prepared as highfructose sugars from corn starch for sweetness An epimer of glucose at C2 Readily converted to glucose in metabolism by isomerization
CH2OH C O HO H H C C C H OH OH

CH2OH

D-fructose

CARBOHYDRATES IN 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.

Fructose forms either

1

CH2OH O H HOH2C 6 OH
5

2C

HO H H

C C C

O H HO
3

1 CH2OH 2

4 5 6

OH

OH

OH

CH2OH

D-fructose (linear)

E-D-fructofuranose

 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.

The formation of hemiketals and hemiacetals results in an asymmetric carbon atom. Isomers that differ only in their configuration about the new asymmetric carbon are called anomers, the new assymetric carbon is called anomeric carbon. a-anomer has the hydroxyl group at the right side of the anomeric carbon F-anomer has the hydroxyl group at the left side of the anomeric carbon

Anomers in aqueous solution freely interconvert between the E and F forms, unless the hydroxyl group attached to the anomeric carbon is linked to another molecule. This process of interconvertion is called MUTAROTATION

EXERCISE
D-Mannose exists in aqueous solution as a mixture of E and F forms. Draw the Haworth projection formula of the two anomers.

Reactions of Monosaccharides

Oxidation-Reduction

 Oxidation

Oxidation using a mild oxidizing agent

Oxidation using a strong oxidizing agent

Oxidation to Uronic Acids

CHO enzymeH OH catalyzed HO H oxidation H OH H OH CH2 OH D -Glu cose CHO OH H OH OH COOH

H HO H H

COOH HO HO

O OH OH

D -Glucu ronic acid (a u ronic acid )

Reduction to alditol

Reduction of ribose to 2-deoxyribose by ribonucleotide reductase

Reaction with dilute base

Reaction with a concentrated base-fragmentation

Esterification

Amino Derivatives

Formation of Glycosides
Treatment of a monosaccharide, all of which exist almost exclusively in a cyclic hemiacetal form, with an alcohol gives an acetal
CH 2 OH O OH H + H H + CH3 OH OH H -H2 O HO H glycos idic H OH CH2 OH bond F-D -Glu copyran os e O OCH 3 H (F-D -Glu cose) H + OH H H HO anomeric carbon

CH2 OH OH H H OH H HO OCH 3

H OH H OH Methyl F-D -glu copyran os ide Methyl E-D -glu copyran os ide (Methyl F-D -glu coside) (Methyl E-D -glucos ide)

Disaccharides

Maltose present in malt, the juice from sprouted barley and other cereal grains maltose consists of two units of Dglucopyranose joined by an E-1,4glycosidic bond maltose is a reducing 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 F -1,4-glycosidic bond to carbon 4 of Dglucopyranose lactose is a reducing 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

Sweeter than sugar, and no calories

N-Glycosides

French Fries a la Plastic

EXERCISE
A. Draw the chair conformations for E-D mannopyranose and F-D-mannopyranose B. Draw the chair conformation of 1. methyl E- and F-D-mannopyranoside 2. E-D-mannopyranosyl-(1-4)- F-Dglucopyranoside

Polysaccharides

Storage Polysaccharides

Glycogen
is the energy-reserve carbohydrate for animals glycogen is a branched polysaccharide of approximately 106 glucose units joined by E-1,4- and E-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

Starch
starch can be separated into amylose and amylopectin amylose is composed of unbranched chains of up to 4000 D-glucose units joined by E-1,4-glycosidic bonds amylopectin contains chains up to 10,000 Dglucose units also joined by E-1,4-glycosidic bonds; at branch points, new chains of 24 to 30 units are started by E-1,6-glycosidic bonds

Structural Polysaccharides

Cellulose
is a linear polysaccharide of D-glucose units joined by F-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 waterinsoluble 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

Plant Polysaccharides

Hemicellulose chains are shorter than cellulose and may be branched

Pectin
Is a heteropolymer containing galacturonate and rhamnose residues Used a gelling agent in the preparation of jams and jellies

Chitin
Present in exoskeletons of arthropods Composed of N-acetylglucosamine, linked in F(1-4)

Bacterial Cell Walls

The bacterial cell wall is a unique structure which surrounds the cell membrane. Maintaining the cell's characteristic shape Countering the effects of osmotic pressure Consist of many layers of peptidoglycan connected by amino acid bridges

Peptidoglycan
is composed of an alternating sequence of Nacetyl-muraminic acid (NAM) and Nacetylglucosamine (NAG) joined by F-1,4glycosidic bonds.

CH 2 OH O O O H 3 C CH C= O NH L A la D Gln NH O= C CH 3 O HO

CH 2 OH O O N O= C CH 3

O L Ly s ( CH 2 ) 4 N H- C-( Gly ) 5 -N H-- -- C= O To tetrapeptide side chains

D A la O N H-( Gly) 5 C- - --

The NAM-NAG polysaccharide is in turn cross-linked by small peptides

in Staphylococcus aureus, the cross link is a tetrapeptide this tetrapeptide is unusual in that it contains two amino acids of the D-series, namely D-Ala and D-Gln each tetrapeptide is cross linked to an adjacent tetrapeptide by a pentapeptide of five glycine units

Bacterial polysaccharides form a biofilm

A biofilm is attached to a surface and harbors a community of embedded bacteria that contributes to biofilm production and maintenance

A Pseudomonas aeruginosa biofilm

Glycoproteins

Components of the cell membrane, where they play variety of roles in cell adhesion

Glycoprotein Functions
Glycoproptein and Cancer Protein Turnover Viral Growth Antifreeze Glycoprotein

Protein turnover is initiated by removal of carbohydrate residues by hydrolysis

Specific enzymes are responsible for oligosaccharide assembly

Glycosyltransferase-catalyzes the synthesis of oligosaccharides through the formation of glycosidc bond

Protein glycosylation takes part in the lumen of the endoplasmic reticulum and in the golgi complex

Processing of an N-linked oligosaccharides

PROTEOGLYCANS contain long glycosaminoglycans

Glycosaminoglycans (GAGs) are anionic polyanionic polysaccharides chains made of repeating disaccharide units
play important roles in the structure and function of connective tissues polysaccharides based on a repeating disaccharide where one of the monomers is an amino sugar and the other has a negative charge due to a sulfate or carboxylate group Glycosaminoglycans tend to be negatively charged, because of the prevalence of acidic groups. GAGs are usually attached to proteins to form proteoglycans

Common GAGs
heparin: natural anticoagulant hyaluronic acid: a component of the vitreous humor of the eye and the lubricating fluid of joints chondroitin sulfate and keratan sulfate: : components of connective tissue

Chondroitin 6-sulfate
The repeating disaccharide units of Nacetylgalactosamine ang glucoronic acid can be sulfated in either 4 or 6 position of GalNAc They are prominent components of cartilage tendons, ligaments and aorta Palate is made from chondroitin sulfate

LECTINS
Proteins that bind specific carbohydrate structures Are ubiquitous, being found in plants, animals and microorganisms