LIPIDS

Triacylglycerols

Phospholipids

Sphingolipids

Cholesterol
STRUCTURE AND PROPERTIES
• soluble in organic solvents (chloroform, tetrachlorocarbon,
acetone, benzene, ethyl ether, etc.)
• insoluble in water and solutions of mineral salts
• Fatty acids have a marked tendency to associate to each other
or with other hydrophobic structures as sterols or hydrophobic
chains of amino acids.

In the organism, lipids fulfill energetic, functional and structural

role.
• Lipid hydrophobicity makes them essential in formation of cell
structures and compartmentalization of some fields in which
distinct metabolic pathways can occur.
• neutral fats (TG) have a very high energetic value 9
kcal/gram,
• role of energetic deposit (in adipose tissue) - TG. For a person
of 70 kg, adipose tissue provides energy needed to survive for
several weeks.
• mechanical role : organs are leaned, or interfering as a buffer
layer to mechanic strains
• thermo insulating role, shrinking the body from cold, and
maintaining the hydric insulation (skin, hair) .
• Certain phospholipids easy and permit the transport of
electrons along the nervous trunk, participating to the
transmission of nervous impulse.
• In biological fluids, lipids can function as transporting system
for nonpolar, liposoluble substances (certain vitamins,
hormones).
• Other lipids, although present in relatively small quantities,
play crucial roles as enzyme cofactors, electron carriers, light-
absorbing pigments, hydrophobic anchors for proteins,
“chaperones” to help membrane proteins fold, emulsifying
agents in the digestive tract, hormones, and intracellular
messengers.
 General classification

glycerides
simple lipids
cerides

glycerophospholipids
complex lipids
sphingolipids
LIPIDS
Fatty acids and alcohols

derivative lipids Steranic compounds

carotenes
Liposoluble vitamins
Fatty acids

• common characteristics:
• aliphatic monocarboxylic acids
• Normal chain, saturated or unsaturated
• Even number of carbon atoms in molecule
(4 to 32 carbon atoms)
- rarely:
• Extra hydroxyl group
• Odd number of carbon atoms
• Branched chain
• Cyclic structure
Saturated fatty acids

No. Common Systematic Melting

Structure
C atoms name name point

4 Butyric acid n-Butanoic acid CH3(CH2)2COOH - 8,0

6 Caproic acid n-Hexanoic acid CH3(CH2)4COOH - 1,5
8 Caprylic acid n-Octanoic acid CH3(CH2)6COOH +16,5
10 Capric acid n-Decanoic acid CH3(CH2)8COOH +31,0
12 Lauric acid n-dodecanoic acid CH3(CH2)10COOH +44,0
14 Myristic acid n-tetradecanoic acid CH3(CH2)12COOH +53,8
16 Palmitic acid n-Hexadecanoic acid CH3(CH2)14COOH +62,5
18 Stearic acid n-Octadecanoic acid CH3(CH2)16COOH +69,6
20 Arachidic acid n-Eicosanoic acid CH3(CH2)18COOH +71,6
22 Behenic acid n-Docosanoic acid CH3(CH2)20COOH +80,3
24 Lignoceric n-Tetracosanoic acid CH3(CH2)22COOH +84,5
acid
Unsaturated fatty acids

Common
Symbol Systematic name Structure
name
Palmitoleic
16:9 Hexadecenoic acid CH3(CH2)5CH=CH-(CH2)7COOH
acid
9-Octadecenoic
18:9 Oleic acid CH3(CH2)7CH=CH-(CH2)7COOH
acid
Nervonic 15-tetracosenoic
24:15
acid acid
9,12-
Linoleic
18:9,12 octadecadienoic CH3(CH2)4(CH=CHCH2)2(CH2)6COOH
acid
acid
9,12,15-
Linolenic
18:9,12,15 Octadecatrienoic CH3CH2(CH=CHCH2)3(CH2)6COOH
acid
acid
5,8,11,14-
Arachidonic
20:5,8,11,14 Eicosatetraenoic CH3(CH2)4(CH=CHCH2)4(CH2)2COOH
acid
acid
 Geometric isomerism

H (CH 2 ) 7 CH3 CH 3 (CH 2 ) 7 H

C C

C C
H (CH 2 ) 7 C O OH H (CH 2 ) 7 C OO H

acid oleic (cis) C18:9 acid elaidic (trans)

(natural) (artificial)

Trans fatty acids are produced by fermentation in the rumen of dairy animals
and are obtained from dairy products and meat. They are also produced
during hydrogenation of fish or vegetable oils. Because diets high in trans
fatty acids correlate with increased blood levels of LDL (bad cholesterol) and
decreased HDL (good cholesterol), it is generally recommended to avoid
large amounts of these fatty acids. Unfortunately, French fries, doughnuts,
and cookies tend to be high in trans fatty acids.
Hydroxylated fatty acids

(CH3–(CH2)21–CH–COOH)
|
OH

cerebronic acid C24

(CH3–(CH2)7–CH=CH–(CH2)12–CH–COOH).
|
OH

hydroxynervonic acid C24:15

 Cyclic fatty acids C20
H
C OOH
7 5 3 1
9
6 4
10
8 2
20
Prostanoic acid
Acid prostanoic
11 12 CH3
14 16 18
H 13 15 17 19

prostaglandine E2

Tromboxan A2

They act as hormones, especially locally

 1 C H 2 O C O R 1

Glycerophospholipids role 2 C H O C O R 2

3 C H 2 O P X

O O –

A. are amphipathic molecules - include in the same molecule two distinct

regions:
• one with hydrophobic character (fatty acid radicals bound to glycerol) and
• a polar one (phosphoryl radical, phosphorylcholine, cholamine, serine and
inositol, respectively).
• ⇒ quality of surfactant (surface-active substance), by targeting them
between a polar aqueous phase and a nonpolar, lipid phase.
• ⇒ permits phospholipids to participate to the structural organization of
biological membranes, where they are associated with proteins.
• ⇒ essential role in the processes of selective permeability.
• are emulsifying agents, capable to form micelles, ⇒ permits water
solubilisation of completely hydrophobic lipids and their transport in
aqueous media.
B. They present amphoteric character, dissociating as amphions.
• ⇒ different electrical charges (plus and minus) ⇒ involved in
supramolecular structures, by forming bonds with other biocomponents of
different chemical nature.
Phospholipids with sphingosine backone =
Sphingolipids
 S
Phosphoyl Fatty
Choline
Acid G
P
L
H
Y
I
C
N
E
Fatty acid G
R
O
O
S
L
I
N Long unsaturated Alcohol
Phosphate
E
Sphingolipids

• are complex lipids having a structural role.

• derivatives of the amino alcohol sphingosine.
• Unlike the other lipids (acylglycerols, glycerophospholipids),
the fatty acid they contain is bound with an amide bond (at the
amino group at C2) and not with an ester bond.
• In most of the cases, the fatty acid has 24 carbon atoms and
can be saturated or unsaturated, even hydroxylated: lignoceric
(C24), nervonic (C24:15), cerebronic (24C atoms and a hydroxyl
group) acids.

• Sphingolipids are subdivided into two categories: with

phosphorus and without phosphorus.
 Sphyngolipids without phosphorus
Ceramides
• found in nervous tissue, liver, spleen
• are present at low levels only in tissues,
• important as intermediates in the biosynthesis of complex sphingolipids
• precursors for a number of sphingolipid metabolites that have important
functions in cellular signaling, including sphingosine-1-phosphate

H
Neutral glycosylceramides (cerebrosides)

- identified in brain, liver, muscles, spleen, erythrocytes

- most widespread are the monoglycosyl-ceramides (or cerebrosides),
- consist of a basic ceramide unit linked at carbon 1 of sphingosine to glucose or
galactose.
- Fatty acids with 24 carbon atoms (lignoceric, nervonic) predominate in ceramides
Sulfatides
• derivatives of cerebrosides.
• Sulfate esters of galactosylceramide and lactosylceramide
(sulfoglycosphingolipids - often referred to as "sulfatides" or
"lipid sulfates"), with the sulfate group linked to position 2, 3 or
6 of the hexose (galactosyl) moiety,
• are major components of brain lipids and they are found in
trace amounts in other tissues.
Gangliosides
• sphingolipids rich in carbohydrate residues.
• found in brain (grey substance), ganglions, spleen and
erythrocytes, in cell membranes, especially of nervous cells, at
the external surface of these membranes.
• total hydrolysis of gangliosides liberates sphingosine, fatty
acids, glucose, galactose, N-acetylgalactosamine and N-
acetylneuraminic acid (sialic acid).
• always a glucose residue is bound to the ceramide
• brain gangliosides consist of about 100 glycosyl residues
• probably a role in nervous impulse transmission.
• Some cerebrosides and gangliosides are involved in blood
group specificity
 Gangliosides:
the most complex sphingolipids

At least one acidic sugar (sialic acids)!

NAN - N-acetylneuraminate
NGN - N-glycolylneuraminate

Glc - glucose
Gal - galactose,
GalNAc - N-acetylgalactosamine,
NAN - N-acetylneuraminate
Sphingolipids with phosphorus
• most important and abundant of sphingolipids.
• predominate in nervous tissue,
• participate to the structure of myelin sheaths of axons,
performing an insulating role, due to their hydrophobic
character
• are constituted of:
• sphingosine,
• a fatty acid mainly with 24 carbon atoms (lignoceric or nervonic) and
• phosphorylcholine (or phosphorylcholamine), bound with an ester
bond to the primary alcohol of sphingosine.
• Sphingosine and the fatty acid radical represent the
hydrophobic component, and phosphorylcholine
(phosphorylcholamine) – the hydrophilic component.
Sphingomyelin
- resembles phosphatidylcholine in many of its physical properties,
- can apparently substitute in part for this in membranes,
- it also has its own unique role - it is a major constituent of the plasma membrane of
cells
Steroid Compounds
• Steroid compounds with hydroxyl functions are found also as esters with
fatty acids (sterides).
• There are several steroids in the biological systems: cholesterol, bile acids,
vitamin D, sex hormones, adrenocortical hormones, sitosterols, cardiac
glycosides and alkaloids.
• contain a cyclic steroid nucleus (or ring) namely
cyclopentanoperhydrophenanthrene
• carbon atoms are not coplanar; hexagon cycles have chair conformation
• can exist as 64 steroisomers
• (C5, C10, C8, C9, C13 şi C14).
 H H H H
A C A C
H H H
B D B D
5 5
H H

H H H

5α - sterane (gonane) 5β - sterane (gonane)

- In nature, there are found only derivatives of two of these – C5

- The configurations of the other 5 centers of isomerism
(C8, C9, C10, C13, C14) are the same for all natural steroids
- If a steroid contains one or more hydroxyl groups
it is commonly known as sterol (means solid alcohol)
 CH3 Steroid basic structures

18C – estrane estrogen hormones

CH3
19C – androstan
CH3 androgen hormones

CH3
21C – pregnane
CH3
corticosteroid and gestagen
CH3 hormones
 H 3C

CH3
CH3

CH3
24C – cholane bile acids

H 3C
CH3
CH3
27C – cholestan
CH3 CH3 cholesterol and other
cholesterol derivatives
Cholesterol
• The main animal sterol.
• It is largely distributed in all cells.
• Structurally, it is ∆5-3β-hydroxycholestan
• is present in higher quantities in nervous system, bile (6 g/l) and egg yolk.
• It contains 27 carbon atoms and the molecular formula is
C27H45–OH;
• It is a cyclic alcohol, the hydroxyl group is bound to C3 in cycle A, position β;
• It is unsaturated, having a double bond in cycle B, position C5 - C6;
• It has 2 methyl radicals (–CH3), C13 and C10, with β orientation (C18; C19);
• In position C17 has a side chain with 8 carbon
21 22
atoms (C20 - C27).
23 26
18 20

12 17 24 25
19 11
C
13 D 16
15 27
14
1 9
2 10 8
A B
3 5 7
4
HO
6
 Cholesterol
Role
- membrane component
- precursor of signal molecules
- steroid hormones
- progesterone
- testosterone
- estrogen
- cortisol.

Transport
LDL (low-density lipoprotein)
uptake by a specific receptor on the cell

Pathology (hypercholesterolemia -> atherosclerosis),

- acquired
- genetic (childhood heart attacks!)
• The presence of cholesterol in the body has exogenous or
endogenous origin.
• is found in free form, and esterified to superior fatty acids,
saturated or unsaturated; this fraction is called esterified
cholesterol
• In blood serum : 150-250 mg/100 ml, one third free and two
thirds esterified
• is a solid, crystalline, white substance,
• insoluble in water (although the –OH group is polar, the rest,
tetracyclic nucleus and the side chain are nonpolar),
• soluble in organic solvents.
• It is optically active, levogyre, and has the hydroxyl group at C3
in β position (that makes it to precipitate with digitonin).
• Its melting point is 148.5°C.
Biochemical role of cholesterol

• Esterified with superior fatty acids, it is found in the

constitution of lipids referred as sterides (frequently with
palmitic, oleic and linoleic acids);
• It participates in the structure of membranes and hence to
their permeability;
• It participates to the formation of plasma lipoproteins;
• It is the primary metabolic precursor of important steroid
derivatives such as bile acids and steroid hormones;
• As 7-dehydrocholesterol is precursor of vitamin D3;
• It participates in the emulsification of lipids at in the intestine,
reducing the superficial tension between water and lipids, as it
has a hydrophilic –OH group.
Other natural sterols in the body

C D C D

H A B H A B
HO HO
H H
α
β
Cholestanol Coprostanol (results in intestine
by microbial action
(trans) (cis)

Ergosterol
Vitamin D
Stigmasterol and
sitosterol are found
HO
mainly in superior plants
 Biological derivatives of sterols
Bile Acids - in intestine intervene in lipid digestion and absorption

C OOH Cholanic acid – basic structure

Primary bile acids – in liver

H
OH

C O OH C O OH

OH OH
HO HO
H

cholic acid chenodeoxycholic acid

(3,7,12-trihydroxycholanic acid) (3,7-dihydroxycholanic acid)
• Primary bile acids are conjugated with glycine (H2N-CH2-CH2COOH) or
taurine (H2N-CH2-CH2-SO3H), forming conjugated primary bile acids:
glycocholic acid, taurocholic acid, glycochenodeoxycholic and
taurochenodeoxycholic acids.
• An amide bond is form during conjugation.

R-CO-NH-CH2-COOH glycocholic acid

R-CO-NH-CH2-CH2-SO3H taurocholic acid

R-CO- cholic acid residue

After their synthesis in liver, primary conjugated bile acids are secreted into
bile, where, in contact with the alkaline pH and ions Na+, K+, they are
transformed in bile salts, as sodium glycocholate, etc.
 • in intestine, part of primary bile acids are modified by intestinal flora, by
deconjugation and 7-dehydroxylation, and form secondary bile acids:
deoxycholic acid, derivative of cholic acid, and lithocholic acid, derivative of
chenodeoxycholic acid – secondary bile acids.

OH

COOH COOH

HO HO
H H

deoxycholic acid lithocholic acid

• Both primary and secondary bile acids and their conjugates form salts in a
weak base medium (pH > 7), bile salts (ex. with Na+ or K+) which are more
soluble than the corresponding acids.
• Primary and secondary bile acids, which have participated in
the small intestine to the food lipid digestion and absorption,
are reabsorbed by intestinal mucosa at ileum level and are
transported through portal vein to liver, at a rate of 98-99%.
• Here, a series of processes takes place: secondary bile acids
are transformed in primary bile acids by hydroxylation at
carbon C7, and then they are conjugated with taurine and
glycine, then secreted again in bile and then in the intestine.
• This circuit is called “enterohepatic circulation" of bile salts.
 Properties and role
Bile acids, their salts are soluble in water
The surfactant, detergent behavior of bile salts is explained by their
three-dimensional molecular model

CH3
CH3

CH3 12

CO

NH
OH
7 CH2
OH
C O OH

OH
Lipid structures with particular
biological significance
Lipoproteins
• proteins in which the prosthetic component has a lipid nature: fatty acids,
triacylglycerols, free and/or esterified cholesterol, phospholipids.
• Involved in the constitution of certain subcellular structures (cell and
mitochondrion membranes)
• serve as vehicles, as in blood plasma, to transport lipids from small intestine to
tissues and from liver to fatty storages of other tissues – classified according to
their density
• The main binding forces between the protein component and the lipid one are
hydrophobic and electrostatic forces; van der Waals forces can also participate
Lipids in cell membrane

• natural membranes are formed of a double phospholipids layer, with

specific proteins and enzymes attached to surface, or spanning the
hydrocarbon layer
• mosaic model
• Biomembranes delimit the internal medium of cell, also the intracellular
particles.
• realize compartmentalization of living matter and have characteristic
properties of selective permeability
• structural stability of biomembranes is realized by two types of
interactions:
• hydrophobic interactions (lipid – lipid);
• electrostatic interactions (lipid-proteins).
mosaic model of cell membrane
Basic characteristics of biomembranes:

• They have the same basic molecular structure;

• They are constituted of lipoprotein complexes;
• Their structure is highly ordered;
• They have stabile structure, ensured by hydrophobic and electrostatic
interactions;
• They have amphipathic character, allowing the transport of polar and
nonpolar substances;
• They function as hemipermeable barriers, with selective character;
• They manifest a high electric resistance;
• They have a thickness of 6-7 nm;
• They are genetically determined;
• They present asymmetry, which would be an important factor in the
unidirectional or vector transport mechanism of certain substances across
the membranes;
• They are self-assembling systems that require minimal energy expenditure.
Roles of membranes:

• To regulate the substance intra- or extra-cellular transport,

functioning as hemipermeable barrier between the external in
internal cell medium;
• They delimit the cell and compartmentalize its interior in
different intracellular organelles;
• They ensure the metabolic homeostasis of cells;
• They contribute to the intracellular coordination of
biochemical processes.

⇒ involvement in the coordination and inter- and intracellular

interactions, at physico-chemical, biochemical and
physiological level
Protein acylation

• binding of fatty acids or lipids that contain phosphoinositol to proteins:

• N-myristoylation,
• glypiation,
• palmitoylation
• Isoprenylation

N-myristoylation
• occurs by binding, through amide linkage, a myristoyl residue CH3-(CH2)12-
CO- to a N-terminal glycine residue of a protein by the action of a specific
enzyme: N-myristoyl transferase.
• occurs in the endoplasmic reticulum during protein synthesis and thus
represents a co-translational change.
• N-myristoylation also allows the anchoring of proteins to the external face
of cell and intracellular membranes
Glypiation
• attachment of a complex structure, which contains a molecule of
glycerophosphoinositol, to a protein.
• takes place in Golgi apparatus, by fixation of the lipid to the C-terminal
extremity of the protein.
• It permits the anchoring of proteins on the external face of cell membrane
or in the interior of intracellular organelles
•
Palmitoylation
• thioester or ester bond between a palmitate residue and a cysteine or, very
rarely, a serine or threonine residue.
• anchors proteins on the internal face of the cell membrane, such as the
transferring receptors.
• in the Golgi apparatus
• its role is not fully established, but its reversibility, unlike other types of
acylation, certainly is an important element of the biological function of
this post-translational modifications.

cysteine serine threonine

Isoprenylation
• fixation of an isoprenic derivative to a cysteine residue, situated at the C-
terminal extremity of certain proteins:
• farnesyl, resulting in the condensation of three molecules of isoprene and
• geranyl-geranyl, resulting in the condensation of four molecules of
isoprene.
• ⇒anchoring of proteins to the internal face of cell membrane.
• proteins encoded by protooncogenes (i.e. RAS)
• A deficit of the geranyl-fixing enzyme was identified in retinal degeneration.

HOOC C C S CH
H
NH2 2

Farnesyl-cysteine
Fatty acids properties

• largely determined by the length and degree of unsaturation of the hydrocarbon

chain.
• The nonpolar hydrocarbon chain accounts for the poor solubility of fatty acids in
water. The longer the fatty acyl chain and the fewer the double bonds, the lower is
the solubility in water.
• The carboxylic acid group is polar (and ionized at neutral pH) and accounts for the
slight solubility of short-chain fatty acids in water.
• Fatty acids with a chain shorter than 12 carbon atoms are soluble in water – an
important fact for the explanation of the differentiation in absorption of lipids.

O .....................HO
R (CH 2) C C (CH2) R
n
O n
OH .....................
Hydrogen bonds
 Chemical properties

Fatty acids react with alcohols, forming esters

O
R' C OOH + H O R R' C + H 20
O R

They form substituted amides with amines

O H

R' C OOH + H 2 N R CH2 OH R' C N R CH2 O H + H 2O

Oxidation of unsaturated fatty acids

oxidation
CH3-(CH2)7-CH=CH-(CH2)7-COOH −-------→

CH3-(CH2)7-COOH + HOOC-(CH2)7-COOH
 In the presence of oxygen, microorganisms and light, free unsaturated acids
or the ones found in lipids are oxidized, forming peroxides or hydroxyperoxides,
unstable compounds ⇒ rancidity
O O OOH H

R C C R 1 + O2 R C C R1 sau R C C R1

H H H H H H

Unsaturated acid peroxid acid hydroperoxid

- These substances are unstable and decompose, forming alcohols,
aldehydes, hydroxyacids, and volatile acids, having unpleasant taste and
smell.
- Condensing products can be also formed, which have a toxic effect on the
organism.

Fatty unsaturated acids can suffer hydrogen addition

CH3–(CH2)7–CH=CH–(CH2)7–COOH + H2 → CH3–(CH2)16–COOH
Alcohols in lipid constitution
- Aliphatic alcohols without nitrogen;
- aminoalcohols (Aliphatic alcohols with nitrogen);
- cyclic alcohols.

Glycerol and derivatives

(1) α CH2 OH HO–CH2–CHOH–CHO D-glyceraldehide

(2) β CH OH HO–CH2–CO–CH2–OH dihydroxyacetone

(3) α ' CH2 OH HO–CH2–CHOH–COOH D- or L-glyceric acid

Long chain alcohols
• Found in cerides (waxes), esterified with fatty acids.
• Monohydroxilic with C16-C32
• Normal chain, even number of carbon atoms

Aminoalcohols
Cholamine (2-aminoethanol or monoethanolamine)

HO CH2 CH C OOH HO CH2 CH2 NH2

- C O2
NH2

Serine Cholamine
It has a basic character in water solution due to the ionization of the amino group.

CH2 OH CH2 OH
+ H O + H
2
CH2 NH2 CH2 N H OH -
H

Choline
+ CH3
HO CH2 CH2 N C H 3 OH - It has a strong basic character
CH3

Acetylcholine, acetic ester of choline, acts as a chemical mediator in the

process of nervous impulse transmission (ex. neuromuscular junction)

+ CH3
H 3C C O CH2 CH2 N CH3 OH - acetylcholine
CH3
O
Serine
HO CH2 CH C OOH

NH2

Sphingosine - insoluble in water but soluble in alcohol, acetone and ether

18 5 4 3 2 1
CH3 ( C H 2 ) 12 CH CH CH CH C H 2 OH

OH NH2

Inositol – cyclic alcohol OH OH

OH

OH mesoinositol
OH

OH
Acylglycerols (triglycerides) esters of glycerol with fatty acids

CH2 O CO R CH2 OH CH2O O CO R1 CH2 O CO R

* C H OH CH O CO R *C H O CO R2 CH O CO R1

CH2 OH CH2 OH CH2 OH CH2 O CO R2

1–monoacylglycerol 2–monoacylglycerol 1,2–diacylglycerol mixed triacylglycerol

CH 2 O CO R CH2 O CO (CH 2)14 CH3

CH O CO R CH O CO (C H2 )16 C H3

CH 2 O CO R CH2 O CO (CH 2)7 CH CH (CH 2)7 C H3

simple triacylglycerol palmito - stearo - oleine

Physical properties
• soluble in organic solvents and insoluble in water ⇒ present no osmotic
problems to the cell, even when stored in large amount
• In aqueous medium form emulsions - important for digestion and
absorption of lipids.

• The melting points depend on their molecular weight and the degree of
unsaturation
• fats and butters – animal triacylglycerols, solid or semisolid, with
melting points between +20°C and +30°C;
• tallows – solid animal triacylglycerols, with the melting points greater
than 35°C;
• oils – vegetal triacylglycerols (except fish oils) which are liquids at room
temperature.

Being mixtures of triacylglycerols, natural fats have no fix melting points,

but melting intervals.
Chemical properties
Hydrolysis
CH 2 O CO R1 C H2 OH R1 C OOH

CH O CO R2 CH OH R2 C OOH
+ 3 H2O → +

CH 2 O CO R3 C H2 OH R3 C OOH

Basic hydrolysis (saponification) will form glycerol and soaps (salts)

CH 2 O CO R C H2 OH

CH OH C OO - + 3 K +
CH O CO R + 3 KO H → +3 R

CH 2 O CO R C H2 OH

- Hydrogen addition to the double bonds (saturation of fats) transforms the

liquid fats (oils) into solid fats (margarine).
- Double bonds in fats can react with iodine. Iodine index (iodine grams used
per 100 grams of fat) gives an indication of the unsaturation degree.
- Under the action of oxygen in the air, radiation or microorganisms,
triacylglycerols suffer a rancidity process
Roles of triacylglycerols (TG)
• especially animal triacylglycerols meet the following functions:
• major energy reserves for the body;
• are thermal and mechanical insulators, having a protective
role of the various organs;
• Combined with proteins as lipoproteic complexes,
triacylglycerols helps in fat transporting in the body.

Cerides (waxes)
• are esters of fatty acids with fatty monohydroxyalcohols (16 to
32 carbon atoms). They are mostly found in vegetal structures,
but also in animals (red blood cell membrane, etc.)

CH3(CH2)mCOO-(CH2)nCH3
 Complex Lipids
lecithins
cephalins
with N
serincephalins
Glycerophospho-
lipids (contain P) plasmalogenes
phosphatidic acids
Complex without N inozitphosphatide
lipids
cardiolipins
with P sphingomielines
Sphingo-
lipids ceramides
(contain N) Without P cerebrozides
sulphatides
ganglyosid
es
GLYCEROPHOSPHOLIPIDS

Fatty acid
G
L
Y
C
Fatty acid E
R
O
L
Phosphate Alcohol
 Glycerophospholipids

1 C H2 O CO R1
Nonpolar hydrophobic
2 CH O CO R2 region Amphipathic
C H2 O P X
Amphionic
3
polar hydrophobic character
O O–
region

- Fatty acids found in glycerophospholipids constitution:

- at least one in unsaturated, usually oleic acid or arachidonic acid,
- the other one can be saturated, frequently palmitic or stearic acid.
- the unsaturated fatty acid esterifies position 2
- Represents the lipids with structural role in cells (membranes)
- Cerebral tissue is characterized by its richer composition in
glycerophospholipids.
- Notable quantities are distributed in erythrocytes, bone marrow, liver,
egg yolk
 Glycerophospholipids without nitrogen

Phosphatidic acids

- acidic character to the molecule, leading to K, Na, Mg, Ca salts

- important in lipids biosynthesis (triacylglycerols and glycerophospholipids)
- found only L-α-phosphatidic acids;
- they present optical isomerism and are part of L-series
 Cardiolipins (diphosphatidylglycerols)

O OH

R1 C O CH2 CH2 O P CH2 O

R2 C O C H OH CH OH O CH O C R3

O CH2 O P O CH2 CH2 O C R4

O O

diphosphatidylglycerol

- found in skeletal muscle, liver, brain, green leaves and bacteria;

- are important components of inner mitochondrial membrane.
- Cardiolipins are the only phosphoglycerides that possess antigenic
properties
 Phosphatidylinositols

- Found in skeletal muscle, brain and cardiac muscle -

- derivatives, having phosphate residues which esterify other
hydroxyl groups of inositol.
- They are precursors of second messengers in cell signaling
 Glycerophospholipids with nitrogen

Choline phospholipids (lecithins)

- have structural role and not a storage one, as acylglycerols.

- Mitochondria and microsomes are very rich in lecithins.
- High quantities are found in egg yolk (10%), cerebral tissue (7%), bone
marrow (5%), and liver (3-4%).
- This type of substances has an amphipathic character and they can
dissociate as acids or bases (amphionic character).
- The body hydrolyses these substances under the action of enzymes called
phospholipases.
Ethanolamine phopholipids (cephalins)

predominate in brain
(13%); liver (6%), kidney
(3%), muscle (1%), yolk

Phosphatidylserine (serine cephalins)

predominate in the brain
tissue, representing 50%
of all glycerophospholipids
 Glyceryl ether phospholipids (plasmalogens)

Glyceryl ether phospholipids contain an ether unit instead of an acyl unit at C1

Alcohol
G
L
Y
C
Fatty acid E
R
O
L
Phosphate Alcohol
 Ether (acetal) lipids (plasmalogens)

- an ether bond or a vinyl ether bond to position 1 of L-

glycerol

“Platelet-activating factor" or 1-alkyl-2-acetyl-

glycerophosphorylcholine can exert profound biological
effects at minute concentrations – inflammatory mediator