CARBOHYDRATE

PROGRAM KBK
FK-UKI

Prof. Dr. Drh. Maria Bintang, MS

Kepala Departemen Biokimia Kedokteran
FK-UKI
 REFERENCES
 Lehninger. 2008. Principles of
biochemistry 5rd Ed.
 Michael W. King. 2006. Medical
Biochemistry.
 Murray R K, Granner D k, Mayers P a &
Rodwell V w. 2009. Harper’s Illustrated
Biochemistry. 28th 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
Monosaccharides can be categorized
according to their value of 'n,'
n Category
3 Triose
4 Tetrose
5 Pentose
6 Hexose
7 Heptose
8 Octose
ALDOSES
KETOSES
CARBOHYDRATE ACCORDING SIMPLE
SUGAR UNITS

Carbohydrates
Monosaccharides Disaccharides Polysaccharides
Glucose Maltose Starch
Galactose Lactose Glycogen
Fructose Sucrose Cellulose
Ribose Cellobiose Hemicelluloce
 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-D-galactosamine)
• 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-D-
galactosamine
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 (structure 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 Monomeric
Linkages
Name Unit
alpha 1->4 links
with extensive
Glycogen D-Glucose
alpha1->6
branches
Cellulose D-Glucose beta 1->4
N-Acetyl-D-
Chitin beta 1->4
glucosamine
alpha 1->4 links
Amylopectin D-Glucose with some alpha 1-
>6 branches
Amylose D-Glucose 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-D-
glucosamine
• 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 acetal linkages are alpha
connecting C 1 of one glucose
Amylopectin 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 (α-D-
glucose) 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. Carbonyl group (alone)
◦ Oxidation to a carboxylic acid group
◦ Reduction to a hydroxyl group
◦ Cyanohydrin reaction (and reaction with other nucleophiles)
2. Hydroxyl groups :
• Ester formation – Oxidation to carbonyl
◦ Ether formation – Reduction to deoxy
◦ Cyclic acetal – Replacement with NH2, SH, or X
3. Both carbonyl and hydroxyl groups
◦ Cyclic hemiacetals (pyranose/furanose)
◦ Formation of acetals (glycosides)
◦ Aldose/ketose isomerizations
 DISEASES OF CARBOHYDRATE
METABOLISM DISODER

1. Diabetes mellitus
2. Lactose intolerance
3. Fructose intolerance
4. Galactosemia
5. Glycogen storage disease
BUKU ACUAN PRAKTIKUM BIOKIMIA
 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) - Waxes
 Conjugated Lipids (polar lipids) :
◦ Phospholipids - Cerebrosides - Sulfolipids
 Derived Lipids:
◦ Fatty acids - Hydrocarbons
◦ Fatty alcohols - Vitamins A, D, E, K
◦ Fatty aldehydes
 Miscellaneous:
◦ Soaps - Oxidative polymers
◦ Coloring matters - Thermal polymers
 Potato Apple Soybean Clover Spinach
Lipid class Rye grass
tuber fruit seed leaves cloroplasts
Monogalactosyldiacylglycerol 6 1 trace 46 39 36

Digalactosyldiacylglycerol 16 5 trace 28 29 20

Sulfoquinovosyldiacylglycerol 1 1 trace 4 4 5

Triacylglycerol 15 5 88

Phosphatidylcholine 26 23 4 7 10 7

Phosphatidylethanolamine 13 11 2 5 5 3

Phosphatidylinositol 6 6 2 1 2 2

Phosphatidylglycerol 1 1 trace 6 7 7

Others 15 42 5 3 4

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 Melt
Structure
Name 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
Oleic CH3(CH2)7CH=CH(CH2)7COOH +16 18:1∆9
Linoleic CH3(CH2)4(CH=CHCH2)2(CH2)6COOH -5 18:2∆9,12
Linolenic CH3CH2(CH=CHCH2)3(CH2)6COOH -11 18:3∆9,12,15
Arachidonic CH3(CH2)4(CH=CHCH2)4(CH2)2COOH -50 20:4∆5,8,11,14
…………… 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 Unsaturated
Palmitic Stearic Oleic Linoleic Other
Animal Origin
Butter 29 9 27 4 31
Lard 30 18 41 6 5
Beef 32 25 38 3 2
Vegetable Origin
Corn oil 10 4 34 48 4
Soybean 7 3 25 56 9
Peanut 7 5 60 21 7
Olive 6 4 83 7 -
 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
in floor,candies,
Carnauba CH3(CH2)28CH2-OH CH3(CH2)24COOH polishes, varnishes,
cosmetic products,
secreted by bees to make
Beeswax CH3(CH2)28CH2-OH CH3(CH2)14COOH
cells for honey and eggs
found in the head
Spermacetic CH3(CH2)14CH2-OH CH3(CH2)14COOH 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 (cholesterol & phospholipid)
• 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 2 C10
sesquiterpenes 3 C15
diterpenes 4 C20
sesterterpenes 5 C25
triterpenes 6 C30
Lipid storage disorder
The body's store of fat is constantly broken down and
reassembled to balance the body's energy needs with the
food available.
Groups of specific enzymes help the body break down
and process fats. Certain abnormalities in these enzymes
can lead to the buildup of specific fatty substances that
normally would have been broken down by the
enzymes.
Over time, accumulations of these substances can be
harmful to many organs of the body.
Disorders caused by the accumulation of lipids are
called lipidosis. Other enzyme abnormalities result in the
body being unable to properly convert fats into energy.
These abnormalities are called fatty acid oxidation
disorders
……….. Lipid storage disorders

Lipid storage disorders (or lipidoses) are a group of

inherited metabolic disorders in which harmful amounts
of lipids (fats) accumulate in some of the body’s cells and
tissues.
Types Lipid storage disorders
Niemann-Pick disease
Fabry disease
Farber’s disease
Gangliosidoses = Tay-Sachs disease
Krabbé disease
Metachromatic leukodystrophy
Wolman’s disease
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 + HO-
OH ® 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&n630/Virt
_Class_2/CHOreactions.htm
http://www.elmhurst.edu/~chm/vchembook/
550lipids.html
http://www.nicerweb.com/bio1151b/Locked/
media/ch05/polysaccharides.html