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CHAPTER 16: CARBOHYDRATES

16.1 Sugars: Their Structures and Stereochemistry

Carbohydrate general formula: Cn(H2O)n


Monosaccharides: simple sugars
Oligosaccharides: linked monosaccharides
Polysaccharides: bonded monosaccharides
One water molecule lost for every monosaccharide added
Polysaccharides are the most commonly encountered carbohydrates
o Ex. (Glycogen animals, Starch & Cellulose plants)
Carbohydrates: major energy sources
Oligosaccharides: cell-cell interactions, immune recognition
Polysaccharides: major structural component of organisms
o Ex. (Cellulose major component of grass & trees, others major components of bacterial cell walls

What is unique about the structures of sugars?


Monosaccharides: building blocks of all carbohydrates, simple sugars
o Aldose polyhydroxy aldehyde, Ketose polyhydroxy ketone
Trioses: simplest monosaccharide, has three carbon atoms
o Ex. Glyceraldehyde (aldotriose), ketotriose
Aldotetroses/Ketotetroses (4), aldopentoses/ketopentoses (5), aldohexoses/ketohexoses (6),
aldoheptoses/ketoheptoses (7)
6-carbon sugars are most abundant in nature
5-carbon sugars occur in RNA (ribose) & DNA (deoxyribose)
4-carbon & 7-carbon sugars play roles in photosynthesis and metabolic pathways
Optical isomers: not superimposable on mirror images
Chiral (asymmetric) carbon: source of optical isomerism
Glyceraldehyde: simplest carbohydrate that has a chiral carbon, exists in 2 isomeric forms
Enantiomers: mirror-image stereoisomers
Configuration: 3D arrangement of groups around a chiral carbon atom
D,L system: denotes stereochemistry
Possibilities for stereoisomerism increase as the number of carbon atom increases
Fischer projection: 2D perspective of the molecular structure, written vertically
Aldoses are more common than ketoses
L or D depends on the arrangement at the chiral carbon with the highest number
D-configuration in Fischer projection: hydroxyl group (-OH) is on the left of the highest-numbered chiral carbon
L-configuration in Fischer projection: hydroxyl group (-OH) is on the right of the highest-numbered chiral carbon
Diastereomers: nonsuperimposable, non-mirror-image
o Aldotetroses: 2 chiral carbons, 4 stereoisomers (2 D & 2 L)
o L-erythrose is the diastereomer of D-/L-threose
Epimers: diastereomers that differ from each in the configuration at only one chiral carbon
D sugars predominate in nature
What happens if a sugar forms a cyclic molecule?
Sugars with 5 or 6-carbon atoms normally exist as cyclic molecules
Cyclization is the result of the interaction between functional groups of different carbons
Hemiacetal: C-1 & C-5 interaction in aldohexoses
Hemiketal: C-2 & C-5 interaction in ketohexoses
Anomeric carbon: the carbonyl atom that becomes the new chiral carbon
Anomers: designated and

In Fischer projection:
o -anomer of a D sugar has the hydroxyl group at the right of the anomeric carbon
o -anomer of a D sugar has the hydroxyl group at the left of the anomeric carbon
Mutarotation: Free carbonyl species can readily form an - or -anomer, can be converted from one form to
another
Only one anomer of -D-ribose (RNA) & -D-deoxyribose exists (DNA)
Hayworth projection formulas: cyclic structures of sugars, planar 5- or 6-membered rings, represent
stereochemistry of sugars
Furanose: 5-membered ring, planar
Pyranose: 6-membered ring, chair conformation
Fischer
Hayworth
o D sugars, right down; left up
Terminal (-CH2OH) is found on the carbon atom with the highest number in the numbering scheme

16.2 Reactions of Monosaccharides


What are some oxidation-reduction reactions of sugars?
Oxidation of sugars: provides energy for organisms, highest yield when they are completely oxidized to CO2 &
H2O (aerobic processes)
Reduction of CO2 & H2O: forms sugars, photosynthesis
Oxidation of aldehyde
carboxyl group; aldoses are reducing sugars
Ketoses can isomerize aldoses and become reducing sugars
Tollens reagent: detects presence of reducing sugars, Ag(NH3)2+, (+) result, silver mirror
In deoxy sugars, hydrogen is substituted for a hydroxyl group in the sugar
Glycoprotein: conjugated proteins that contain some carbohydrate group, in addition to the polypeptide chain
Carbonyl group of sugar reduced to hydroxyl
alditols (polyhydroxy alcohols)
Alditols are used commercially as sweeteners in sugarless gum or candy
o Ex. Xylitol xylulose, sorbitol sorbose
What are some important esterification reactions of sugar?
Phosphate esters
o Usual intermediates when carbohydrates are broken down to provide energy
o Formed by transfer of a phosphate group from ATP to give the phosphorylated sugar and the ADP
Important in the metabolism of sugars
What are glycosides, and how do they form?
Glycosidic linkage: formed when a hydroxyl group (ROH) bonds to an anomeric carbon to react with another
hydroxyl group
Glycosidic linkage is not an ether because it can be hydrolyzed to original alcohols; involves the anomeric carbon
of the sugar in its cyclic form
Full acetal/Glycoside: a hemiacetal carbon + alcohol
Glycosidic bond: bonds in a full acetal/glycoside, (OCH3), basis of formation of polysaccharides &
oligosaccharides
O-glycosides: each sugar bonded to an oxygen atom of another molecule
Furanosides: glycosides derived from furanoses
Pyranosides: glycosides derived from pyranoses
-D-glucose sugars: (1
4) & (1
6)
-D-glucose sugars: , (1 1)
Chemical natures depend on which monosaccharides are linked together & also on the particular glycosidic
bond formed
Linear: internal 2 glycosidic bonds
Branched-chain: 3 glycosidic bonds

If the end residue is a free hemiacetal, it will test positive as a reducing sugar
Biochemical Connections: Vitamin C is related to sugars
Vitamin C (ascorbic acid): unsaturated lactone with a 5-membered ring
Each C is bonded to an OH except for the carboxyl group involved with the cyclic ester bond
Air oxidation of Vit. C
hydrolysis of ester bond: loss of activity as a vitamin
Vitamin C deficiency
scurvy
Scurvy: defects in collagen structure cause skin lesions & fragile blood vessels
Hydroxyproline: necessary for collagen stability because of the hydrogen-bonded cross-links between collagen
strands
What are some other important derivatives of sugar?
Amino sugars: an amino group (NH2) instead of a hydroxyl group (OH) of the parent sugar
N-acetyl amino sugars: contains an acetyl group (CH3CO)
o Ex. N-acetyl--D-glucosamine & N-acetyl--D-muramic acid (has an added carboxylic chain) found in
bacterial cell walls (peptidoglycan)
16.3 Some Important Oligosaccharides
Disaccharides: 2 monosaccharides linked by a glycosidic bond
o Ex. Sucrose, Maltose, Lactose, Isomaltose, Cellobiose
What makes sucrose an important compound?
Sucrose
o Common table sugar, extracted from sugarcane & sugar beets
o -D-glucose (aldohexose, pyranose) + -D-fructose (ketohexose, furanose)
o ,(1 2)
o Non-reducing sugar; glucose & fructose are reducing sugars singly
o Hydrolyzed when consumed to provide energy
Fructose: sweeter than sucrose, smaller amount can produce same sweetness as sucrose
Saccharin: artificial sweetener, caused cancer to laboratory animals
Sucralose: Splenda, cannot be metabolized by the body, has galactose derivative, safe sugar substitute
Biochemical Connections: Fruits, Flowers, Striking Colors, and Medicinal uses too
N-glycosides: sugar binds to the nitrogenous & aromatic base as found in ATP, vitamins, DNA & RNA
Anthocyanins: sugar derivatives of red & blue colored flowers, water-soluble, polar
Cinnamaldehyde (cinnamon) & vanillin (vanilla)
Digitalis: prescribed for irregular heartbeat
Laetrile: benzaldehyde derivative with a glycosidic linkage to glucuronic acid, thought to fight cancer with
cyanide moiety
Biochemical Connections: Lactose Intolerance: Why do so many people not want to drink milk?
Sugar intolerance: inability to digest or metabolize sugars
Lactose: milk sugar
Deficiency of the enzyme lactase causes buildup of lactose in the stomach
Bacterial lactase reaction digestive problems: bloating & diarrhea
Galactosemia: if the enzyme that catalyzes a subsequent reaction in the pathway is missing, galactose builds up
Severe problem for infants, causes swelling: when brain is affected, retardation might happen
Are there any other disaccharides important to us?
Lactose
o -D-galactose + -D-glucose
o (1 4); since galactose is a C-4 epimer of glucose
o Reducing sugar

Maltose
o Obtained from the hydrolysis of starch
o 2 residues of D-glucose in an (1 4)
o Used in beverages such as beer & milk
Cellobiose
o Obtained from hydrolysis of cellulose
o 2 residues of D-glucose in a (1 4)

16.4 Structures and Functions of Polysaccharides


Polysaccharide: many monosaccharides linked together
Homopolysaccharide: only one monosaccharide makes up a polymer
Heteropolysaccharide: consists of more than one type of monosaccharide
Glucose is the most common monomer
Frequently, only two types of molecules in a repeating sentence
-glycosidic linkages: cellulose & chitin (structural materials)
-glycosidic linkages: starch & glycogen (carbohydrate storage)
How do cellulose and starch differ from one another?
Cellulose
o Major structural component of plants (wood & plant fibers)
o Linear homopolysaccharide of -D-glucose: (1
4)
o Hydrogen-bonded, with extensive intra & intermolecular forces
o Fully extended conformation with alternating 180o flips of glucose units
Cellulase: majority of animals lack this enzyme that hydrolyze cellulose to glucose
Cattle have this to digest hay and grass; termites have this to digest wood
Is there more than one form of starch?
Starch: polymers of -D-glucose that occur in plant cells (starch granules in cytosol)
Amylose: linear polymer of glucose, (1
4) linkages, helix (6 residues per turn)
Amylopectin: branched chain polymer, (1
6) & (1
4)
-amylase: exoglycosidase, cleaves at the nonreducing end of the polymer
maltose
-amylase: endoglycosidase, hydrolyze a glycosidic linkage anywhere
glucose + maltose
Amylopectin is not completely degraded because the branching linkages are not attacked
Debranching enzymes: occur in plants & animals, attack at the (1
6) linkages
How is glycogen related to starch?
Glycogen
o Branched-chain polymer of -D-glucose, (1
6) & (1
4) linkages
o More highly branched than amylopectin
o Branches: every 10 residues of glycogen
o 13 glucose residue with 12 layers of branching
o Found in animal cells as glycogen granules: liver & muscle cells
Glycogenin: found in every glycogen molecule
Glycogen phosphorylate: cleaves one glucose at a time from the nonreducing end of a branch to produce
glucose-1-phosphate
More branched = more water soluble, more targets for glycogen phosphorylate to allow faster mobilization of
glucose
What is chitin?
Linear homopolysaccharide of N-acetyl--D-glucosamine: (1
4)
Structural role: fair amount of mechanical strength hydrogen bonds

Major structural component of exoskeleton of invertebrates: insects & crustaceans + algae, yeast, fungi
What role do polysaccharides play in the structure of cell walls?
Heteropolysaccharides are major components of bacterial cell walls
(1
4) linkages of N-acetyl-D-glucosamine & N-acetylmuramic acid
N-acetylmuramic acid has a lactic acid side chain [OCH(CH3) COOH] on C3; found only in prokaryotic cell walls
Staphylococcus aureus has an oligomer of 4 amino acids (tetramers) which is bonded to N-acetylmuramic acid;
this is cross-linked by another 5 amino acids (pentaglysine)
Bacterial cell walls are one of the few places where D-amino acids occur in nature; this protects bacteria from
hydrolysis
Cross-linking of polysaccharides make up the peptidoglycan
Pectin: made up mostly of D-galacturonic acid, derivative of galactose
Lingnin: major non polysaccharide component in plant cell walls, polymer of coniferyl alcohol; tough & durable
material
Plant cell walls contain little peptide or protein
Do polysaccharides play any specific roles in connective tissue?
Glycosaminoglycans: polysaccharide based on a repeating disaccharide in which one of the sugars is an amino
sugar and at least one of them has a negative charge(sulfate or carboxyl group)
Heparin: natural anticoagulant, helps prevent blood clots
Hyaluronic acid: vitreous humor of the eye & lubricating fluid of joints
Chondroitin sulfates & keratin sulfate: components of connective tissue
Glucosamine sulfate & chondroitin sulfate: help repair frayed or damaged cartilage, knees
16.5 Glycoproteins

Glycoproteins: contain carbohydrate residues in addition to the polypeptide chain, involved in immune response
o Ex. Antibodies bind to and immobilize antigens
o Antigenic determinants antigenic molecule that antibodies recognize to which they bind

How are carbohydrates important in the immune response?


Antigenic determinants are found in human blood groups: A, B, O, AB
Distinctions depend on the oligosaccharide portions of the glycoproteins on the surface of blood cells
N-Acetylgalactosamine: nonreducing end of type-A blood-group antigen
-D-galactose: type-B blood-group
In type-O blood, neither are present; while in type-AB blood, both are present
Proteoglycans: eukaryotic cell membrane recognition, extremely high carbohydrate content, constantly
synthesized & broken down,
Hurlers syndrome: accumulates large amounts of amino sugars leading to skeletal deformities, severe mental
retardation, death in early childhood