Carbohydrates

Carbohydrates linked to lipids glycolipids

Carbohydrates linked to proteins glycoproteins

Biological roles of these molecules:

1. Components of cell walls, and extracellular structures in plants,
animals and bacteria
2. Involved in biological processes of recognition between cell
types and recognition of cellular structures by other molecules

Characteristic chemical features of carbohydrates:

1. The existence of at least one and often 2 or more asymmetric centers
2. The ability to exist in linear or cyclic structures
3. The ability to form polymeric structures via glycosidic bonds
4. The potential to form multiple hydrogen bonds with water or other
molecules in their environment
Carbohydrates = polyhydroxy aldehydes or
polyhydroxy ketones
Three groups of carbohydrates
1. Monosaccharides simple sugars, (CH2O)n, cannot
be broken down into simple sugars at mild
conditions
2. Oligosaccharides 2 to 20 monosaccharides linked
by glycosidic bonds with the loss of water every time
a monosaccharide is added, disaccharides are more
common
oligo = few
3. Polysaccharides polymers of the simple sugars
and their derivatives
I. Monosaccharides 3 to 7 carbon atoms, sweet,
water-soluble
Aldoses and ketoses = what type of carbonyl group
Trioses, tetroses, pentoses, hexoses, heptoses = number of carbons

Then: aldotriose, ketotriose, aldohexose, ketohexose, etc

Simplest sugars
Stereochemistry
Enantiomers
Diastereomers stereochemical isomers that differ in one or two chiral
centers
Epimers diastereomers isomers that differ only in one chiral center

D-eryhthrose L-erythrose D-erythrose D-threose

enantiomers diastereomers
epimers
 Structures and stereochemical
relationships of D-aldoses having
three to six carbons.

D-glucose and D-
mannose = epimers
D-glucose and D-
gulose are just plain
diastereomers
Structures and stereochemical
relationships of D-ketoses having
three to six carbons.
D- and L-designations

D-eryhthrose L-erythrose

Fischer projection formulas

Cyclic structures and anomers

-D-Glucopyranose is a
special epimer of -D-
glucopyranose (anomer)
Glucose and ribose can cyclicize in two ways
Mutarotation conversion of one anomer into the other

Specific rotation of
either anomer upon
standing is
 Chair is more stable

If all bulky groups in chair

are in equatorial positions
= stable
Derivatives of Monosaccharides
1. Sugars with free anomeric OH are good reducing agents of H2O2, ferricyanide,
certain metals (Cu2+ and Ag+) = reducing sugars
Fehlings, Benedicts, Barfoeds = Cu2+ (Cu2O formation = brick red ppt
Tollens = Ag+ (silver mirror)

Aldonic acids are produced: Ex. glucose to gluconic acid

2. Enzymatic oxidation of C-6 position for aldohexoses = uronic acids

Ex. Glucose to glucuronic acid

3. Oxidation at C-1 and C-6 gives = aldaric acids

Ex. Glucose to glucaric acids
4. Mild reduction of the carbonyl group of aldoses and ketoses gives
sugar alcohols or alditols = sweet tasting

Sorbitol, mannitol and xylitol = sweeteners in sugarless gums and mints

5. Deoxy sugars

Ex : deoxyribose (systematic name = 2-deoxy-D-

erythropentose)
6. Sugar esters of phosphoric acid
7. Amino sugars

Chitin components (as N-

acetyl derivatives)
8. Acetals, ketals and glycosides
glycosides
-OH of carbohydrates (usually the anomeric) and OH of
another source (carbohydrate or any alcohol) to form a
glycosidic bond with the elimination of water
II. Oligosaccharides
Usual monosaccharides that make up oligosaccharides and
polysaccharides = glucose, fructose, mannose and galactose
(hexoses), ribose and xylose (pentoses)
Disaccharides = simplest oligosaccharides

(No free anomeric OH)

Maltose and cellobiose
are both disaccharides of
glucose
Difference: Maltose has
the -1,4 glycosidic bond
while cellobiose has the -
1,4 glycosidic bond
Both are reducing sugars
Sucrose has an -1,2 glycosidic
bond. It is a non-reducing sugar
because the anomeric OH of -
glucose is bonded to the anomeric
OH of fructose

Trehalose has an -1,-1

glycosidic bond, also non-
reducing. It is found n organisms
subject to temperature variations
and other environmental
stresses. The blood sugar of
insects.
Shorthand notation: Glc1-4Glc or
Glc-4Glc
Complete name: O--D-
glucopyranosyl-(14)-D-
glucopyranose

Shorthand notation: Glc1-4Glc or

Glc-4Glc
Complete name: O--D-
glucopyranosyl-(14)-D-
glucopyranose
Hydrolysis of sucrose

-D-glucose -D-fructose

Net = -39.5

Enzyme is invertase bec. of the change in optical rotation upon hydrolysis

Sucrose can be hydrolyzed also by dilute acid, and sucrase in the

human intestine.
Higher oligosaccharides
Oligosaccharides as antibiotics

Bleomycin A2
Aburamycin C

Streptomycin
Sulfurmycin B
III. Polysaccharides or Glycans
Homopolysaccharides or homoglycans cellulose or (14)-D-
glucopyranan, starch,
glucans, mannans, etc.
Heteropolysaccharides pectins (arabinose, galactose and
galacturonic acid)

Polysaccharide functions:
storage materials starch, glycogen
structural components cellulose, chitin
protective substances mucopolysaccharides like hyaluronic
acids as protective coatings on animal cells
Storage polysaccharides

a) starch

-(14)

-(16)

The two components of starch, amylose and amylopectin. Amylose is

about 100-1000 residues long while amylopectin (300-6000 residues) has
branching at the -(16) every 12 or 20 units. Starch is stored in the
chloroplasts (where photosynthesis takes place) and in amyloplasts
(specialized starch storage bodies).
b) Glycogen storage polysaccharide in animals, like amylopectin but
more branched, with branching every 8 to 12 glucose units

c) Dextran main linkage is (16), but may have 12, 13, or 14

Structural polysaccharides
a) Cellulose -(14) glucose linkage, most abundant carbohydrate polymer

amylose cellulose

Amylose in starch have bent -(14) linkages so must adopt a

helical configuration. Cellulose, on the other hand, can adopt a fully
extended conformation by alternating 180 flips of the glucose units.
Thus H-bonding is maximized and is responsible for the greaat
strengths of tree trunks.

Cellulose is not digested in the human body but ruminants and

termites contain bacteria that contain cellulase that can catalyze
the removal of glucose units
The structure of cellulose showing interchain H-bonding which
strengthens the structure.
b) chitin

Where cellulose sheets are in parallel packing, chitin can have three
possible packing arrangements.
-chitin is parallel, -chitin is anti-parallel while -chitin involves pairs
of parallel sheets separated by one anti-parallel sheet.

Chitin is the second most abundant carbohydrate polymer

3. Alginates -

alginates

Like cellulose, chitin,

mannans and poly(D-
mannoronate) form
extended H-bonds.
Poly(-L-guluronate) dimerize with Ca2+ ions forming a structure
known as egg carton.
4. Agar composed of agarose and agaropectin, composed of alternating D-
galactose and 3,6-anhydro-L-galactose with side chains of 6-methylgalactose
Agarose is neutral while agaropectin is charged bec. of sulfation and
COO-

The ability of agarose to form complex

bundles to fom gels in aqueous solns make it
useful in numerous chromatographic
procedures including size-exclusion
chromatography and electrophoresis.

Agarose double helix

5. Carrageenan similar to agar except that instead of the L-galactose
moiety, it is D-galactose. Much sulfated than agar.

Carrageenan is used mainly for thickening, suspending and gelling.

Used as binder to cooked meat, to firm sausages and as a thickener in
toothpaste and pudding.
 6. Glycosaminoglycans components of proteoglycans, consist of linear
chain of repeating disaccharides in which one of the monosaccharide unit
is an amino sugar and the other negatively charged because of the
presence of sulfate or carboxylate group.

Chondroitins and Heparin natural

keratan sulfate are anticoagulant
found in tendons, substance
cartilage and other
connective tissue

Hyaluronate
component of the
vitreous humor in the
eye, and in synovial
fluid, the lubricant fluid
of joints in the body

Dermatan sulfate
extracellular matrix of
skin