Chapter 10 Carbohydrates

Cn(H2O)
m
Simple sugars: monosaccharides carbohydrates: Cn(H2O)m

simplest trioses
sugars: sugars
3 carbon with
atoms 3 carbon
atoms

+ alcohol group -OH

carbonyl group
can be
carbohydrates are:
two types:
- highly polar

- soluble in water

- several chiral carbon

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Stereochemistry of carbohydrates: Focus on enantiomers; epimers; anomers

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Stereochemistry of carbohydrates

3-carbon sugar, 1 chiral carbon. Two isomers.

D- and L-configuration

To determine which is the D- or which is the L-configuration in a

solution, a polarimeter is used.

Rationale: Enantiomers change the direction of plane polarized

light that passes through a solution.
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Stereochemistry of carbohydrates when there are more than 1 chiral carbon

Epimers : differ only at 1 of several chiral carbon atoms

note
where
the
numbering
of carbon
atoms
start

D-Glucose and D-Mannose are epimers (because of C-2).

D-Glucose and D-Galactose are epimers (because of C-4).
Why are D-Mannose and D-Galactose NOT epimers?

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Common monosaccharides: no need to memorize structures
but know names of these sugars
- how many carbon chain
- and which one is a ketose

five
carbon
chain
sugars
pentose

six
carbon
chain
sugars

hexose

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Cyclization of monosaccharides
Alcohol group reacts with an aldehyde group within sugar chain
forming a new chiral carbon, C1, creating a new stereoisomer.
C1 is the anomeric carbon. The a and b forms are anomers.

these are anomers

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Cyclization of fructose, a ketose:
1. C-5 alcohol reacts with the C-2 keto group to form alpha- or beta-D-fructofuranose

2. If C-6 alcohol reacts with the C-2 keto group, D-fructopyranose forms.

High fructose corn syrup & glucose isomerase:

In solution, these cyclic forms of fructose are in equilibrium. D-fructopyranose is more stable at high temperatures, and
tastes ‘sweeter’ than glucose. High fructose corn syrup, found in processed food that is sweet – soda, candies, cereals,
etc – is made in an industrial scale by turning glucose from corn into fructose by using the enzyme glucose isomerase.

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 Mutarotation
When pure a-anomer in water, will eventually become a mixture of
a- and b-anomers

H2O
36% a-anomer

pure 100% a-anomer

in water
64% b-anomer
after equilibrium
will become a mixture of
a- and b-anomers
at equilibrium
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Names of the cyclic forms of monosaccharides are based on the
names of these rings

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Cyclic form of monosaccharides can be in Chair or Boat conformation.
Equatorial bonds & Axial bonds
big groups prefer to be in equatorial bonds to minimize steric clash
chair form is preferred to minimize steric clash

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Reducing and nonreducing sugars

A test for the presence of glucose in blood: Fehling’s test.

glucose reacts with Cu2+ ions (blue in solution) to form a red precipitate.

glucose

sugars with aldehyde group = reducing sugars

sugars with keto group = nonreducing sugars

example: fructose
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Sugars can be modified by functional groups, including other sugars:

O-glycosidic bond anomeric carbon atom to –OH group of another molecule

forming a glycoside

N-glycosidic bond anomeric carbon atom to an amine

Carbohydrates also form ester linkages to phosphates.

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These are some of the functional groups that can modify sugars:
methyl acetylamine carboxyl phosphate

How will you recognize sialic

acid from this group?
(look for a unique functional
group found only in sialic acid)

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Formation of disaccharides and oligosaccharides: glycosidic bond
between sugar monomers

glucose glucose

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maltose (a disaccharide)
Common disaccharides no need to memorize structures
but, need to know names, and the
constituent monosaccharides

milk

sucrose: glucose + fructose

lactose: glucose + galactose
maltose: glucose + glucose
beer

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 polysaccharides

glycosyltransferases enzymes needed for biosynthesis of polysaccharides

(catalyze the formation of glycosidic bonds)

substrate :

uridine diphosphate (UDP)

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polysaccharides

homopolymer

heteropolymer

Examples polymers of glucose:

a. Glycogen used for energy storage
b. Starch used for energy storage
c. Cellulose function: structural

These polymers of glucose

have different structures.
Why different in properties & If cellulose is a glucose polymer,
function? why can’t humans digest cellulose?

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Branching in polysaccharides a-1,4- is for linear
a-1,6- is for branching

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homopolymer of D-Glucose: starch & glycogen function: energy storage

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starch

Amylose linear polymer of glucose α-1, 4-glycosidic bonds

Amylopectin branched polymer branching α-1, 6-glycosidic bond for

every 30 α-1, 4-glycosidic bonds

glycogen

linear α-1, 4-glycosidic bonds

branching more branching than starch

α-1, 6-glycosidic bond

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Cellulose homopolymer of D-glucose function: structural

Virtually all the -OH groups in cellulose form hydrogen bonds, within the chain
and between chains. This makes cellulose ‘strong’ (unlike starch).

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 Glycoprotein: protein + sugars/carbohydrates

Three main classes:

1. Glycoproteins more protein by weight

cell-cell recognition, signaling

2. Proteoglycans more sugar by weight

specific type of polysaccharide glycosaminoglycan
structural role, lubricants

3. Mucins or mucoproteins mainly carbohydrates by weight

protein is characteristically attached to the
carbohydrate by N-acetylgalactosamine
lubricants

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 N-linked glycoprotein O-linked glycoprotein

What Ser, Thr

amino acids
are sugars
attached to
in glycoproteins?

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The pentasaccharide core of N-linked glycoproteins:
3 mannose + 2 modified glucose (N-acetylglucosamine)

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The surface of HIV is coated with carbohydrates (attached to a protein, gp120)
gp120 ‘gp’ = glycoprotein 120 kDa in size

carbohydrates
gp120

www.bio.davidson.edu/Courses/Molbio
www.bioch.ox.ac.uk scanlan group

The carbohydrates are variable, hence, the surface of HIV looks ‘different’.
Anti HIV vaccines have failed because of this variability due to carbohydrates.
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Another example of glycoprotein
Erythropoietin stimulates the production of red blood cells

Glycosylation of erythropoietin enhances the stability of the protein in the blood.

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 charge: negative
Glycosaminoglycans
functional groups:
sulfate, carboxyl
(repeating units of
these disaccharides)
function mainly in lubrication,
joints, cartilage

used as anti-coagulant
during surgery

adulterated heparin=
deaths

glycosaminoglycans + proteins = proteoglycans

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 Cartilage

proteoglycan
absorbs water (shock absorber)

chondroitin sulfate

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another example of function of glycosaminoglycan: Chitin
exoskeleton of insect

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 N-acetylgalactosamine
Blood groups
antigens are based galactose
on the different
glycosylation
pattern on the surface
red blood cells.

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Asn Ser, Thr

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Lectins, selectins, and proteoglycans in the extracellular matrix

Integrin and fibronectin, are proteins that

bind carbohydrates. They are considered
lectins.
 
Integrins are on the cell-surface. Their
function is to connect to the actin filament of
the cytoskeleton, and the extracellular matrix
(by binding to fibronectin and proteoglycans).
 
Fibronectin is in the extracellular matrix,
together with proteoglycans and collagen.
 
Actin is a fibrous protein -- protein component
of the cytoskeleton of cells.

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Role of Selectin, Integrin, and Glycoproteins in the migration of leukocytes, for
example, during wound healing:

Selectins proteins on surface of cells that bind to carbohydrates

selectins are subgroup of lectins
selectins are involved in cell adhesion, they are also known as CAMs
(cell adhesion molecules)
P-selectin is a particular selectin involved in migration of leukocytes
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How do we get the flu?
Example: H5N1 (bird flu)
What does H5N1 mean when describing a
flu variant?

Influenza virus binds to a particular sugar on

the surface of our cells – Sialic acid.

Two proteins on the surface of influenza virus:

Hemagglutinin: Binds to sialic acid on
the surface of human cells to gain virus
entry

Neuraminidase: Cleaves the glycosidic bond

to release new virions to infect new cells.
There are parts of these proteins (H and N) that
are highly variable in amino acid sequence.
H5N1, refers to variants in the hemagglutinin
and neuraminidase proteins for a particular
viral isolate.

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