Reference: Nelson, D. L., & Cox, M. M. (2008). Principles of Biochemistry, Fifth Edition. New York: W H.

Freeman
and Company

CARBOHYDRATES

I. 7.1 Monosaccharides and Disaccharides

A. Two Families of Monosacharides are aldoses and ketoses
1) Colorless, crystalline solid soluble in water polar
2) Simplest triose: glyceraldehyde, dihydroxyketone
3) Naming: aldo/keto+affix+oses
B. Monosaccharides have asymmetric center
1) Asymmetric chiral carbon atoms optically active isomeric forms
2) Fischer projection formula
i. Vertical project behind
ii. Stereoisomers = 2n, where n = chiral centers
3) Perspective formulas
i. Most distant chiral C from carbonyl has same as D-glyceraldehyde = D-isomers (natural) OH on the
right
ii. L-arabinose
4) Aldopentose (ribose) + ul = ketopentose (ribulose)
5) Epimers = differ only in 1 C
i. Glucose and mannose C-2
ii. Glucose and galactose C-4

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C. Common monosaccharides have cyclic structures
1) In aqueous solution, if >5C, occurs in cyclic
i. Carbonyl group forms covalent bond of a hydroxyl group
ii. Alcohol + aldehydes/ketones = hemiacetals/hemiketals

Pyranoses 6 mem or ; more stable, must have at least 5 C (C-5 to C-1)

Furanoses 5 mem (C-5 to C-2)
iii. Anomers and *
isomeric forms of monosaccharides that differ only in their configuration about the hemiacetal or
hemiketal C (anomeric carbon)

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 *

interconvert in aqueous solution by a process called mutarotation

identical optical properties
2) Haworth perspective formulas*

D. Organisms Contain a Variety of Hexose Derivatives

1) Amino sugars: C-2 becomes NH2. If + acetic acid = N-acetylglucosamine
2) Deoxy sugars: substitution of a hydrogen for the hydroxyl group at C-6

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 3) Aldonic acid: oxidation of carbonyl C
4) Uronic acid: C-6
5) Saccharic/Aldaric acid: both
6) Carboxylic acid groups of the acidic sugar derivatives are ionized at pH 7: glucuronate, galacturonate
E. Monosaccharides Are Reducing Agents
1) Oxidizing agents: Fe3+ and Cu2+
2) Estimate concentration of sugar
F. Disaccharides contain a glycosidic bond
1) Covalent: hydroxyl group of one sugar reacts with the anomeric carbon of the other
2) readily hydrolyzed by acid but resist cleavage by base

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 3) glycosidic bond protects the anomeric carbon from oxidation

4) Reducing end: end of a chain with a free anomeric carbon

5) Name: /-D/L-nonreducing residue-pyrano/furano-syl-(14 Cs joined by glycosidic bonds)-D/L-
reducingend-ose
6) Lactose = Gal(14)Glc
7) Glycosides: Nonreducing disaccharides
i. Sucrose = Glc(12)Fru or Fru(21)Glc, anomeric carbons involved in glycosidic bond
ii. Trehalose = Glc( 11)Glc

II. 7.2 POLYSACCHARIDES

A. Glycans
1) Homopolysaccharide fuels (starch and glycogen); structural (cellulose and chitin)
2) Heteropolysaccharide extracellular support
i. Peptidoglycan bacterial cell envelope rigid layer
ii. Animal tissues, holds matrix
iii. program for polysaccharide synthesis is intrinsic to the enzymes that catalyze the polymerization of
the monomeric units, and there is no specific stopping point in the synthetic process
B. Some Homopolysaccharides Are Stored Forms of Fuel
i. Heavily hydrated, lots of OH, to H-bond with water
ii. S and G ingested in the diet are hydrolyzed by -amylases, enzymes in saliva and intestinal secretions
that break (14) glycosidic bonds between glucose units

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 1) Starch
i. made in the chloroplast from D-glucose formed photosynthetically
ii. Amylose - long, unbranched chains of D-glucose residues connected by (14) linkages
iii. Amylopectin - (14); the branch points (occurring every 24 to 30 residues) are (16) linkages
2) Glycogen
i. main storage polysaccharide of animal cells formed in cytosol
ii. like amylopectin but more extensively branched and more compact
iii. has as many nonreducing ends as it has branches, but only one reducing end
iv. use as energy source: remove one at a time from nonreducing end
v. not in monomeric form bs osmolarity
3) Dextrans
i. bacterial and yeast polysaccharides made up of (16)-linked poly-D-glucose
ii. with branches
iii. Dental plaque, formed by bacteria growing on the surface of teeth
iv. Size exclusion chromatography: cross-linked to form insoluble materials of various porosities,
admitting macromolecules of various sizes
B. Some Homopolysaccharides Serve Structural Roles
1) Cellulose
i. fibrous, tough, water-insoluble substance found in cell walls of plants
ii. linear, unbranched homopolysaccharide, consisting of 10,000 to 15,000 D-glucose units
iii. configurations rigid chair structures can rotate relative to one another with H-bond crosslinks

iv. cannot be a fuel source for mammals since lack an enzyme to hydrolyze the (beta14) linkages
Termites intestinal tract harbors a symbiotic microorganism, Trichonympha, that secretes cellulase
which hydrolyzes
Wood-rot fungi and bacteria also produce cellulose
2) Chitin

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 i. linear homopolysaccharide composed of N-acetylglucosamine residues in linkage
ii. replacement of the hydroxyl group at C-2 with an acetylated amino group
C. Steric Factors and Hydrogen Bonding Influence Homopolysaccharide Folding
1) Homopolysaccharides fold in three dimensions. The chair form of the pyranose ring is essentially rigid, so
the conformation of the polymers is determined by rotation about the bonds to the oxygen on the
anomeric carbon. Starch and glycogen form helical structures with intrachain hydrogen bonding; cellulose
and chitin form long, straight strands that interact with neighboring strands.
D. Bacterial and Algal Cell Walls Contain Structural Heteropolysaccharides
1) Bacterial and algal cell walls are strengthened by heteropolysaccharides
2) Peptidoglycan in bacteria
i. GlcNAc(14)Mur2Ac; in agarose, it is D-Gal(14)3,6-anhydro-L-Gal.
ii. N-acetylglucosamine and N-acetylmuramic acid residues
iii. Lysozme hydrolyzes the glycosidic bond

3) Agar in red algae

i. sulfated heteropolysaccharides made up of D-galactose and an L-galactose derivative ether-linked
between C-3 and C-6
ii. unbranched polymer agarose (gel-forming) + branched component, agaropectin
E. Glycosaminoglycans Are Heteropolysaccharides of the Extracellular Matrix
1) one of the two monosaccharide units is a uronic acid and the other an N-acetylated amino sugar

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 2) Glycosaminoglycans are attached to extracellular proteins to form proteoglycans
i. Hyaluronic acid (alternating residues of D-glucuronic acid and N-acetylglucosamine)
ii. chondroitin sulfate, dermatan sulfate, keratan sulfate, and heparin
3) Sulfate esters on some of the hydroxyl groups give these polymers a high density of negative charge,
forcing them to assume extended conformations. Then provide viscosity, adhesiveness, and tensile
strength to the extracellular matrix.

III. 7.3 Glycoconjugates: Proteoglycans, Glycoproteins, and Glycolipids

A. Glycoconjugate
1) Biologically active molecule = informational carbohydrate + protein or lipid
2) information carriers: they serve as destination labels for some proteins and as mediators of specific cell-
cell interactions and interactions between cells and the extracellular matrix
3) Specific carbohydrate containing molecules act in cell-cell recognition and adhesion, cell migration
during development, blood clotting, the immune response, and wound healing
B. Proteoglycans
1) Glycosaminoglycan covalent with membrane protein
2) Major components of connective tissue such as cartilage, in which their many noncovalent interactions
with other proteoglycans, proteins, and glycosaminoglycans provide strength and resilience
C. Glycoproteins
1) oligosaccharides of varying complexity joined covalently to a protein
2) outer face of the plasma membrane, in the extracellular matrix, and in the blood
3) less monotonous than proteo
4) rich in information, forming highly specific sites for recognition and high-affinity binding by other
proteins
D. Glycolipids
1) membrane lipids in which the hydrophilic head groups are oligosaccharides
2) act as specific sites for recognition by carbohydrate-binding proteins
E. Summary
Proteoglycans are glycoconjugates in which a core protein is attached covalently to one or more large
glycans, such as heparan sulfate, chondroitin sulfate, or keratan sulfate. The glycan is the greater portion
(by mass) of the molecule. Bound to the outside of the plasma membrane by a transmembrane peptide or
a covalently attached lipid, proteoglycans provide points of adhesion, recognition, and information
transfer between cells, or between the cell and the extracellular matrix.
Glycoproteins contain covalently linked oligosaccharides that are smaller but more structurally complex,
and therefore more information-rich, than glycosaminoglycans. Many cell surface or extracellular proteins
are glycoproteins, as are most secreted proteins. The covalently attached oligosaccharides influence the
folding and stability of the proteins, provide critical information about the targeting of newly synthesized
proteins, and allow for specific recognition by other proteins.
Glycolipids and lipopolysaccharides are components of the plasma membrane with covalently attached
oligosaccharide chains exposed on the cells outer surface.
IV. SUMMARY 7.4 Carbohydrates as Informational Molecules: The Sugar Code
Monosaccharides can be assembled into an almost limitless variety of oligosaccharides, which differ in the
stereochemistry and position of glycosidic bonds, the type and orientation of substituent groups, and the

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 number and type of branches. Oligosaccharides are far more information-dense than nucleic acids or
proteins.
Lectins, proteins with highly specific carbohydrate-binding domains, are commonly found on the outer
surface of cells, where they initiate interaction with other cells. In vertebrates, oligosaccharide tags read
by lectins govern the rate of degradation of certain peptide hormones, circulating proteins, and blood cells.
The adhesion of bacterial and viral pathogens to their animal-cell targets occurs through binding of lectins
in the pathogens to oligosaccharides in the target cell surface. Lectins are also present inside cells, where
they mediate intracellular protein targeting.
X-ray crystallography of lectin-sugar complexes shows the detailed complementarity between the two
molecules, which accounts for the strength and specificity of their interactions with carbohydrates.
Selectins are plasma membrane lectins that bind carbohydrate chains in the extracellular matrix or on the
surfaces of other cells, thereby mediating the flow of information between cell and matrix or between
cells.
V. 7.5 SUMMARY Working with Carbohydrates
Establishing the complete structure of oligosaccharides and polysaccharides requires determination of
branching positions, the sequence in each branch, the configuration of each monosaccharide unit, and the
positions of the glycosidic linksa more complex problem than protein and nucleic acid analysis.
The structures of oligosaccharides and polysaccharides are usually determined by a combination of
methods: specific enzymatic hydrolysis to determine stereochemistry and produce smaller fragments for
further analysis; methylation analysis to locate glycosidic bonds; and stepwise degradation to determine
sequence and configuration of anomeric carbons.
Mass spectrometry and high-resolution NMR spectroscopy, applicable to small samples of carbohydrate,
yield essential information about sequence, configuration at anomeric and other carbons, and positions of

glycosidic bonds.

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