Sunteți pe pagina 1din 58

What We Crave:

Carbohydrate
Human Biochemistry
HCD 12103

A day without carbs is a boring day

Carbohydrate hydrates carbon


General formula = (CH2O)n, n 3
Subdivided into:
Monosaccharide: 3-9 carbon atom
Disaccharides: 2 monosaccharide units
joined
Oligosaccharides: 2-10
Polysaccharide: >10

The sweetest topic:


monosaccharide

Properties of monosaccharide
Recognize by ose suffix
Eg: aldose a monosaccharide where
the carbonyl group is aldehyde
Eg: ketose a monosaccharide where
the carbonyl group is ketone
Sub-classified by number of carbons:
i.e. tri (3), tetr- (4), pent-(5),.

Flash back..
Carbonyl group: O
C
A

aldehyde: O
ketone:

C
H

Classification of
Monosaccharides
Aldohexose (e.g., glucose)
have an aldehyde group at
one end.
H
H
HO
H
H

C
C
C
C
C

Ketohexose (e.g., fructose)


have a keto group,usually
at C2.

C H 2O H
C

OH
H
OH
OH

C H 2O H

HO

OH

OH

C H 2O H

They contain one or more


chiral carbon
Chiral carbon- have four different
groups attached, with no double
bond
make it optically active, rotating
polarized light in different direction,
having different activity in biological
system

LEARNING CHECK
Determine if there is a chiral carbon in
each compound
CI

CI
CH3

CH3

CH2CH3

How many chiral carbon?

Stereoisomer
Stereoisomer
isomeric molecules that have the
same molecular formula and
sequence of bonded atoms, but differ
only in the 3-D orientations of their
atoms in space
DO NOT confuse with structural
isomer

Stereoisomer
Can be devided into
enantiomer, diastereomer
and epimer
Enantiomer
2 stereoisomers that
related to each other by a
reflection: they are mirror
image, non-superimposable

Enantiomers

Enantiomers

Enantiomer
(mirror
image
s
isomers)

Enantiomers

Important properties of
enantiomers
Same physical properties (melting
point, boiling point, etc. except
the interaction with polarized
light.
Same chemical properties except
when another chiral molecule is
involved.

FISCHER PROJECTIONS
Represent mirror images (enantiomers)
in two dimension.
Place the carbonyl group at or near the
top and the last achiral CH 2OH at the
bottom.
If hydroxyl (OH) on highest numbered
chiral carbon
to the right - D-isomer
to the left L-isomer
Most naturally occurring sugars are
D isomers

FISCHER PROJECTIONS

Diastereomers
Stereoisomer not related
through a reflection
operation.
Not mirror image of each
other

A pair of
enantiomers

D-ribose and D-arabinose are diastereomers


because they are isomers but not mirror
images.

Important properties of
diastereomers
Different physical properties.
Different chemical / biological
properties.

The number of stereoisomers is 2n,


where n is the number of chiral
carbon
The 6-C aldoses have
4 chiral carbon.
n=4
24 = 16 stereoisomers

Epimers
Diastereomers that differ the
configuration at single asymmetric
carbon atom.

D-glucose

D-galactose

D-glucose and D-galactose are C-4 epimers

The most stable monosaccharide


structures: pyranose and furanose
forms
< 1% monosaccharides (5C) exist
in open-chain (acyclic) form
Tend to form very stable ring
structure via internal hemiacetal or
hemiketal formation.

The ring formation process is known


as internal cyclization of
monosaccharide
Cyclization involves rxn between
carbonyl group and highestnumbered chiral carbon, producing
hemiacetal or hemiketal

Hemiacetal formation
An aldehyde can react with an
alcohol to form a hemiacetal.

Hemiketal formation
A ketone can react with an
alcohol
to form a hemiketal.

If resulting ring has:


six members (5 carbons & 1 oxygen)
Pyranose
ring
five members (4 carbons & 1
oxygen)
Furanose
ring

Haworth Projection
A way of representing a cyclic (closed
chain) carbohydrate.

Substituents can either point up or


down on this ring.

Haworth Projection

Ribose (5C-aldose) forms either:


a 6-member pyranose ring, by reaction of the C1
aldehyde group with the OH on C5, or
a 5-member furanose ring, by reaction of the C1
aldehyde group with the OH on C4.

Furanose
form

Pyranose
form

Fructose (6C-ketose) forms either


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.

Carbonyl carbon becomes a new


chiral centre.
anomeric carbon
atom. (carbon 1 of an aldose or at carbon 2 of a
ketose)

These structures are designated the


or configurations of the sugar.

Beta & Alpha, -D-glucose are diastereomers


that are called anomers.

-anomer is when OH is occurs on the right


-anomers is when OH is occurs on the left

Haworth projection

Mutarotation
The and anomers interconvert in
solution by maturation.
This process requires that the ring
structure open to the linear form
during the interconversion.

Mutarotation

Chemical properties of
monosaccharide
Many aldoses are reducing sugar (reducing
agent)
Test for reducing sugarFehlings or
Benedicts solution, to check glucose in
urine of diabetic
Monosaccharide + methanol + HCl
glycosidic bond
Once glycoside forms, the ring is locked,
will not reopenno mutarotation

The chemistry of Benedicts Test

Reducing sugars, those that contain a free aldehyde


group, are oxidized by Cu2+which is reduced to Cu1+
and precipitates in a form of a red Cu2O.

Monosaccharide
derivatives

Acids and Lactone


In the presence of oxidizing agents, metal ions such
as Cu+2, and certain enzymes,
undergo oxidation reactions.
Aldehyde group
aldonic acid
Terminal CH2OH group
uronic acid
Aldehyde + CH2OH
aldaric acid
Carbonyl groups in both aldonic and uranic acids can
react with an OH group at the same
molecule to form a cyclic ester
lactone

Oxidation products of glucose

D-Gluconic acid

D-Glucuronic acid

D-Glucaric acid

The beginning of life: ribose


and deoxyribose
D-ribose and D-deoxyribose are important
components of nucleic acids
Present in furanose ring form, with anomer

Keeping it
simple:disaccharides
Consist of 2 monosaccharides bonded
together.
Lactose, sucrose, maltose
Contain glycosidic bond

Notice that
each
disaccharide
has at least 1
glucose
molecules

Formation of lactose

Formation of sucrose

This saccharide does not have a reducing end.


non reducing sugar

Sugars joining hands:


Oligosaccharide
Contain of 3 to 10 monosaccharides unit.
e.g.
Raffinose
Stachyose

Formation of raffinose

3 unit of monosaccharide

Formation of Stachyose

4 unit of monosaccharide

Starch and
Cellulose:Polysaccharide
2 most important polysaccharide are
starch and cellulose
Both are D-glucose polymers
Difference:linkages between glucose
units
Starchmaltose
Celluloselactose

Bread, pasta and potatoes:


Starches
Polymer of -D-glucose
3 common types:
amylase,amylopectin and glycogen
Useful in storing glucose
Give intense dark blue color in the
presence of iodine

Keeping the termites


happy:Cellulose
Similar to starch, except that the
linkages are (1-4) glucose
Useful for structure
Cleavage of linkages with enzyme
produced by certain bacteria (in
termites and ruminant) or fungi
One of the most abundance
biochemicals on earth

Biological connective
tissue:Acidic polysaccharides
CT holds our parts together
Includes tendons, ligaments and
collagen
One of component of polymer is
amino sugar
Examples: hyaluronate and heparin

glycoprotein
Most proteins occuring in blood serum
are glycoproteins
Protein + carbohydrate glycoprotein
In general, linkage is by attachment to
asparagine, serine or threonine
residue.
Appear in some soluble proteins and
membrane proteins.

S-ar putea să vă placă și