CARBOHYDRATE

PROGRAM KBK
FK-UKI

Prof. Dr. Drh. Maria Bintang, MS

REFERENCES
Lehninger.

2000. Principles of
biochemistry 3rd Ed.
Michael W. King. 2006. Medical
Biochemistry.
Murray R K, Granner D k, Mayers P a &
Rodwell V w. 2003. Harpers Illustrated
Biochemistry. 26th Ed.
Pratt,C.W.and Cornely K. 2004. Essential
Biochemistry. Wiley International Edition.
Stryer, Lubert 1995. Biochemistry.4th Ed.

CARBOHYDRATE DEFINITION
Latin

word " sacchararum" = sweet taste of

sugars.
It means a "hydrate of carbon with formula of
carbohydrate isCx(H2O)y (classic)
It is that the compounds are polyhydroxy
aldehydes or ketones (modern)
Initially synthesized in plants
by photosynthesis.

CARBOHYDRATE FUNCTIONS
Source

energy : Glucose, fructose and starch

Store energy : starch in plants or glycogen in animals
and humans
Provide energy through metabolism pathways and
cycles
Form structural components in plant cells and tissues
: cellulosa
Carrier genetic information : DNA, RNA

CARBOHYDRATE CLASSIFICATION

According to the number of individual simple sugar

units : Mono, di and polysaccharides
According to the functional groups :
Aldoses, contain the aldehyde group : glucose, galactose,
ribose.
Ketoses contain the ketone group : fructose
Reducing, sugars oxidized by Tollens' reagent (or Benedict's
or Fehling's reagents) : glucose, galactose, fructose, maltose,
lactose
Non-reducing, sugars not oxidized by Tollens' or other
reagents : Sucrose and all polysaccharides

ALDOSES

KETOSES

CARBOHYDRATE ACCORDING SIMPLE

SUGAR UNITS
Carbohydrates
Monosaccharides Disaccharides Polysaccharides
Glucose
Galactose

Maltose
Lactose

Starch
Glycogen

Fructose

Sucrose

Cellulose

Ribose

Monosaccharides can be categorized

according to their value of 'n,'
n
3
4
5
6
7
8

Category
Triose
Tetrose
Pentose
Hexose
Heptose
Octose

Derivatives of Monosaccharides

Acids and Lactones : made by mild oxidation of an

aldose, (to form an aldonic acid)
Alditols : made by reducing the carbonyl group of a
sugar and resulting polyhydroxy compounds are called
alditol (erythritol, D-mannitol, and D-glucitol/ sorbitol)
Amino Sugars : made by replacing a hydroxyl of a sugar
with an amine group (beta-D-glucosamine and beta-Dgalactosamine)
Glycosides formed by elimination of water between the
anomeric hydroxyl of a cyclic monosaccharide and the
hydroxyl group of another compound

Formed an aldonic acid

beta-D-glucosamine and beta-Dgalactosamine

Glycoside

Cyclic Forms of Monosaccharides

Structural

form of many
monosaccharides may be that of a
cyclic hemiacetal.
Five and six-membered rings are
favored over other ring sizes because
of their low angle and eclipsing strain
Cyclic structures of this kind are
termed
Furanose (five-membered)
or pyranose (six-membered)

Haworth formula

Pyranose forms of hexoses

Oligosaccharides
Glycosidic

bonds between monosaccharides give

rise to oligosaccharides and polysaccharides.
The simplest oligosaccharides, the disaccharides :
sucrose, lactose,trehalose, maltose,gentiobiose,
and cellobiose.
Oligosaccharides are also found as part of
glycoprotein and play a role in cell
recognition/identity

Disaccharides

Polysaccharides

Polysaccharides are polymers of monosaccharide

units
The monomeric units of a polysaccharide are
usually all the same (homopolysaccharides),
though there are exceptions
(heteropolysaccharides).
It differ in the composition of the monomeric unit,
the linkages between them, and the ways in which
branches from the chains occur

.. Polysaccharides

Polysaccharides homopolysaccharides:
Glucose : glucans (structura in fungi, glucoses
joined by beta 1->3 or beta 1->6 bonds )
Mannose : mannans
Xylose : xylans ( polymers of D-xylopyranose)

Polysaccharides heteropolymers :
Glucopyranose and mannopyranose joined by beta 1>4 linkages with beta 1->6 branches to other
substituents.
The glucomannans and xylans are often grouped
together and called hemicellulose.

Polysaccharides

Structures and Roles of some Polysaccharides

Polysaccharide
Name

Monomeric
Unit

Glycogen

D-Glucose

Cellulose

D-Glucose
N-Acetyl-Dglucosamine

Chitin
Amylopectin

D-Glucose

Amylose

D-Glucose

Linkages
alpha 1->4 links
with extensive
alpha1->6
branches
beta 1->4
beta 1->4
alpha 1->4 links
with some alpha 1>6 branches
alpha 1->4

Polysaccharide polymers

Polysaccharides

.. Polysaccharides

Polysaccharides for energy storage in almost all higher

organisms : Animals use glycogen, Plants use starch
(amylose and amylopectin).
Plants use different polysaccharides : cellulose for
structural purposes in their cell walls.
The exoskeleton of many arthropods and mollusks is
composed of chitin, polysaccharide of N-acetyl-Dglucosamine
The most important compounds in this class, cellulose,
starch and glycogen are all polymers of glucose

 Glycogen

is a storage
Carbohydrate found in animals
Starch is a storage
Carbohydrate found in plants
Cellulose
Plant is a structural
carbohydrate (woody
material, cotton fibers)
It is rather insoluble and
most animals cannot
digest cellulose
All of these are polymers of
glucose

Starch
Major

carbohydrate reserve in plant tubers and seed

endosperm where it is found as granules
Stored in chloroplastsof plants
The largest source of starch is corn (maize),wheat,
potato, tapioca and rice
Consists of two types of molecules:
amylose (normally 20-30%)
amylopectin (normally 70-80%)

. Starch

Starch

stored
in chloroplastsof plants
Amylopectin (without
amylose) be isolated
from 'waxy' maize
starch and amylose
(without amylopectin)
isolated after
specifically hydrolyzing
the amylopectin with
pullulanase

Amylose
Forms

a colloidal dispersion in hot water

whereas amylopectin is completely insoluble
Long polymer chains of glucose units connected
by an alpha acetal linkage
All of the monomer units are alpha -D-glucose,
and all the alpha acetal links connect C 1 of one
glucose to C 4 of the next glucose

The

Amylopectin

acetal linkages are alpha

connecting C 1 of one glucose
to C 4 of the next glucose
The branches are formed by
linking C 1 to a C 6 through an
acetal linkages.
Has 12-20 glucose units
between the branches.
Natural starches are mixtures
of amylose and amylopectin.
In glycogen, the branches
occur at intervals of 8-10
glucose units, while in
amylopectin the branches are
separated by 10-12 glucose
units.

Cellulose
Polysaccharide

polymer consisting linear with many

glucose monosaccharide units
long polymer chains of glucose units connected by
a beta acetal linkage so it is makes it different from starch
All of the monomer units are beta-D-glucose, and all the
beta acetal links connect C 1 of one glucose to C 4 of the
next glucose
Cellulose is a major component of the cell walls plants,
and is difficult to digest by human because lacking
enzymes to breakdown the beta acetal linkages

Cellulose:

Beta glucose is
the monomer unit in
cellulose, as a result of the
bond angles in the beta
acetal linkage, cellulose is
mostly a linear chain.
Starch: Alpha glucose is the
monomer unit in starch, as a
result of the bond angles in
the alpha acetal linkage,
starch-amylose actually
forms a spiral much like a
coiled spring.

Compare Cellulose and Starch Structures

Cellulose structure

Glycogen
Polymers

consisting monosaccharide units (-Dglucose) connected by an alpha acetal linkage

All the alpha acetal links connect C 1 of one glucose
to C 4 of the next glucose and branches are formed
by linking C 1 to a C 6 through an acetal linkages
The branches occur at intervals of 8-10 glucose units,
while in amylopectin the branches are separated by
12-20 glucose units.
synthesized and stored mainly in the liver and the
muscles

Structure of Glycogen

CARBOHYDRATE IMPORTANT REACTIONS

1.

2.

3.

Carbonyl group (alone)

Oxidation to a carboxylic acid group
Reduction to a hydroxyl group
Cyanohydrin reaction (and reaction with other nucleophiles)
Hydroxyl groups :
Ester formation
Oxidation to carbonyl
Ether formation
Reduction to deoxy
Replacement with NH2, SH, or X
Cyclic acetal
Both carbonyl and hydroxyl groups
Cyclic hemiacetals (pyranose/furanose)
Formation of acetals (glycosides)
Aldose/ketose isomerizations

LIPID
PROGRAM KBK
FK-UKI

Prof. Dr. Drh. Maria Bintang, MS

Definition of Lipid
Lipids

: hydrophobic or
amphipathic small molecules that
may originate entirely or in part by
carbanion-based condensations of
thioesters (fatty acids, polyketides,
etc.) and/or by carbocation-based
condensations of isoprene units
(prenols, sterols).
Lipids are biomolecules which are
insoluble in water but soluble in
organic solvents like ether and
chloroform.

The functions of lipids

source of energy for the body.
parts of the membranes found within and
between each cell
In the myelin sheath that coats and protects
the nerves
Organ padding
Body thermal insulation
Hormone synthesis
Fat soluble vitamin absorption

Classification of Lipids
Simple

Lipids :

Neutral fats (Triglycerides)

Conjugated

Lipids (polar lipids) :

Phospholipids

Derived

- Waxes

- Cerebrosides

- Sulfolipids

Lipids:

Fatty acids
Fatty alcohols
Fatty aldehydes

- Hydrocarbons
- Vitamins A, D, E, K

Miscellaneous:

Soaps
Coloring matters

- Oxidative polymers
- Thermal polymers

Potato
tuber

Apple
fruit

Soybean
seed

Clover
leaves

Rye grass

Spinach
cloroplasts

Monogalactosyldiacylglycerol

trace

46

39

36

Digalactosyldiacylglycerol

16

trace

28

29

20

Sulfoquinovosyldiacylglycerol

trace

Triacylglycerol

15

88

Phosphatidylcholine

26

23

10

Phosphatidylethanolamine

13

11

Phosphatidylinositol

Phosphatidylglycerol

trace

Others

15

42

Lipid class

Table The lipid class compositions (weight % of the total

lipids) of various plant tissues

Simple Lipids
These

are esters of fatty

acids with various types
of alcohol, distinguished
into fats and oils
Fats are esters of fatty
acids and glycerol.
A fatty acid is an organic
acid with a hydrocarbon
chain ending in a
carboxyl (COOH) group

Fatty acid
Fatty acids are merely carboxylic acids with long
hydrocarbon chains with length may vary from 10-30
carbons (most 12-18)
A fatty acid : Saturated and unsaturated
Saturated if there are no double bonds between carbons of
the molecular chain
ex : Palmitic acid (16 C) and stearic acid (18 C).
Unsaturated if one (mono) or more (poly) double bonds
occur between the carbon atoms of the chain
ex : oleic acid (18 C,1 double bond) , linoleic acid (18 C,2
double bond) and linolenic acid (18 C,3 double bond)

Saturated

unsaturated

Acid
Name

Structure

Melt
Point Symbol

SATURATED
Lauric

CH3(CH2)10COOH

+44

12:0

Palmitic

CH3(CH2)14COOH

+63

16:0

Stearic

CH3(CH2)16COOH

+70

18:0

UNSATURATED
18:19

Oleic

CH3(CH2)7CH=CH(CH2)7COOH

Linoleic

CH3(CH2)4(CH=CHCH2)2(CH2)6COOH

-5

18:29,12

Linolenic

CH3CH2(CH=CHCH2)3(CH2)6COOH

-11

18:39,12,15

Arachidonic

CH3(CH2)4(CH=CHCH2)4(CH2)2COOH

-50

20:45,8,11,14

+16

 Fatty acid

The

unsaturated fatty acids have

lower melting points than the
saturated fatty acids.
The geometry of the double
bond is almost always a cis
configuration in natural fatty
acids.
These molecules do not "stack"
very well. The intermolecular
interactions are much weaker
than saturated molecules.
As a result, the melting points
are much lower for unsaturated
fatty acids.

Triglycerides / triacylglycerol
(TAG)
Main

constituents of vegetable
oils and animal fats
Have lower densities than water
At normal room temperatures
may be solid ("fats" or "butters" )
or liquid (oils)
A chemical compound formed
from one molecule of glycerol
and three fatty acids

Biosyntesis triacylglycerol
pathway

Percent Fatty Acid Present in

Triglycerides
Fat or Oil

Saturated
Palmitic

Stearic

Unsaturated
Oleic

Linoleic

Other

Animal Origin
Butter

29

27

31

Lard

30

18

41

Beef

32

25

38

Vegetable Origin
Corn oil

10

34

48

Soybean

25

56

Peanut

60

21

Olive

83

Wax
A simple

lipid which is an ester of a long-chain alcohol

and a fatty acid
Found in nature as coatings on leaves and stems.
Prevents the plant from losing excessive amounts of water.
Example : Carnuba, Beeswax, Spermacetic
Many of the waxes mentioned are used in ointments, hand
creams, and cosmetics.
Paraffin wax, used in some candles, is not based upon the
ester functional group, but is a mixture of high molecular
weight alkanes.
Ear wax is a mixture of phospholipids and esters of
cholesterol.

WAXES
Wax

Alcohol

Fatty Acid

Used

Carnauba

CH3(CH2)28CH2-OH CH3(CH2)24COOH

in floor,candies,
polishes, varnishes,
cosmetic products,

Beeswax

CH3(CH2)28CH2-OH

secreted by bees to make

cells for honey and eggs

CH3(CH2)14COOH

Spermacetic CH3(CH2)14CH2-OH CH3(CH2)14COOH

found in the head

cavities and blubber of
the sperm whale

Phosphoglycerides or Phospholipids
Esters

of only two fatty

acids, phosphoric acid
and a trifunctional
alcohol - glycerol
Characterized : fatty
acid chain and the
phosphate/amino alcohol
The long hydrocarbon
chains of the fatty acids
are of course non-polar
Structure of a phospholipid, phosphatidate

Phosphoglycerides or Phospholipids

The

phosphate group has a negatively charged

oxygen and a positively charged nitrogen to make
this group ionic
There are other oxygen of the ester groups, which
make on whole end of the molecule strongly ionic
and polar
There are two common phospholipids:
Lecithin contains the amino alcohol, choline.
Cephalins contain the amino alcohols serine or
ethanolamine

Lecithin
Found

in egg yolks, wheat

germ, and soybeans
Extracted from soy beans for
use as an emulsifying agent in
foods
Major component in the lipid bilayers of cell
membranes
Lecithin contains the ammonium salt of choline
joined to the phosphate by an ester linkage

Cephalins
Posphoglycerides

that contain ehtanolamine or the

amino acid serine attached to the phosphate group
through phosphate ester bonds
Found in most cell
membranes, particularly
in brain tissues
Important in the blood
clotting process as they
are found in blood
platelets

Steroids
Derivatives

of terpenes have
tetracyclic skeleton, consisting
of three fused six-membered
and one five-membered ring
are lipids with the principle
function of signaling chemical
biological activities.
Widely distributed in animals
Include such well known
compounds as cholesterol, sex
hormones, birth control pills,
cortisone, and anabolic
steroids

Steroid hormone

Terpenes
A majority

of these compounds are found only in

plants, but some of the larger and more complex
terpenes (squalene & lanosterol ) occur in animals
Considered to be made up of isoprene ( more
accurately isopentane ) units, an empirical feature
known as the isoprene rule
Classification

Isoprene Units

Carbon Atoms

monoterpenes

C10

sesquiterpenes

C15

diterpenes

C20

sesterterpenes

C25

triterpenes

C30

THE AND

1. Carbonyl group

a. Oxidation to a carboxylic acid group Tollens test

Fehlings test

Glucose

oxidase

Glucose to glucitol (sorbitol)

b. Carbonyl group reduction

Periodate oxidation
can be used to quantitatively measure the
number of adjacent hydroxyls in a molecule.
It is used in the determination of
polysaccharide structure
The reaction is most rapid at pH 3-5

c. Oxidation of non-anomeric hydroxyl

groups

Hydrogen

peroxide

A non-specific oxidant
Depolymerizes oligo- or
polysaccharides
Involves a free radical
mechanism
Employs an Fe+2 catalyst
Fe+2 + HOOH Fe+3 + HO. + OH-

Esters

Reaction of alcohol with acid anhydride

or acid chloride forms an ester
Usually done in the presence of a base
such as triethylamine, pyridine, sodium
acetate, sodium hydroxide, (know as
the Schotten-Bauman technique) and is
done to shift the equilibrium toward the
product ester

2. Hydroxyl groups

Use of acid anhydrides

Etherification

of some polysaccharides
Modifies their properties
Makes them more useful
Examples (derivatives of cellulose)
Methyl (-CH3)
Carboxymethyl (-CH2COO-Na+)
Hydroxypropyl (-CH2CH(OH)CH3)

Etherification

Cyclic acetals
The

hydroxyl groups on carbohydrates react

with aldehydes or ketones to form cyclic
acetals
Common carbonyl compounds include acetone
and benzaldehyde
Sometimes such acetals occur naturally, as in
xanthan gum

http://www.cfs.purdue.edu/class/f&n6
30/Virt_Class_2/CHOreactions.htm
http://www.elmhurst.edu/~chm/vchembook/5
50lipids.html
http://www.nicerweb.com/bio1151b/Locked/
media/ch05/polysaccharides.html