BIOCHEMISTRY

VITAMINS
and
LIPIDS
 Vitamins
fat soluble water soluble
 Vitamin A (Wald’s visual cycle)

Retinol (vitamin A alcohol)

Retinal (vitamin A aldehyde)
Retinoic acid (vitamin A
acid) β-carotene (provitamin
A)
Carotenes are hydrolysed by
β-carotene 15-15‘-dioxygenase
Vit.A released from liver as free retinol, and
transported in the plasma by the plasma
retinol binding protein associated with pre-
albumin, target tissues cells contain
cellular retinol binding protein.
George Wald (NP1968)
rods and cones (types of retina cells)
Rods are involved in dim light vision, cones
 Vitamin D

Ergocalciferol (plants)
and Cholecalciferol (in
animals) are sources for
vitamine D activity and
are reffered to as
provitamins. Vitamine D
is regarded as sun-shine
vitamine.
Concentration of 1,25-
DHCC is regulated by
plasma calcium and
phosphate. Low plasma
phosphate increase the activity of
25-hydroxycholecalciferol 1-
hydroxylase. Low plasma calcium
enhances the production of
parathyroid hormone, which in
turn activate 1-hydroxylase.
Vitamin E Anti-sterility vitamin
(group of tocopherols:
α, β, γ, δ etc.
derivatives of 6-
hydroxy chromane
[tocol] ring)
α-tocopherol is most active.
Most of the function are released
to its antioxidant property –
preventing the non-enzymatic
oxidation by molecular oxygen
and free radicals. Protecta the
polyunsaturated fatty acids from
peroxidation reactions – it acts as
a scavenger and gets itself
oxidized (to quinon form).
 Vitamin K1(philoquinone, menaquinone, menadone)

Vitamine K required for the

production of blood clotting
factors, essencial for coagulation (in
German-Koagulation – hence the name K
for this vitamine. It brings about the post-
translational (after protein biosynthesis in
the cell) modification of certain blood
clotting factors. Also acts as a coenzyme for
the carboxylation of glutamic acid residues
present in the proteins and this reaction is catalysed by
a carboxylase (microsomal). It involves the conversion of
glutamate (Glu) to γ-carboxyglutamate (Gla) and requires
vitamin K, O2 and CO2. The formation of Gla is inhibited by
dicumarol, and anticoagulant found in the spoit sweet clover
(Warfarin is its synthetic analogue)
Vitamin B1 (Thiamine, Thiamine pyroposphate [TPP])

anti-beri-beri vitamin
The alcohol (OH) group of
thiamine is esterfied [catalysed
by thiaminepyrophosphate transferase] with

two phosphate
forming coenzyme
thiamine
pyrophosphate (TPP)
 Vitamin B1(Biochemical functions)

1.The enzyme pyruvateBiochemical functions

dehydrogenase catalyses (oxidative
decarboxylation) the irreversible conversion of pyruvate to acetyl CoA.
This reaction is dependent on TPP (thiamine pyrophosphate), besides
the other coenzymes.
2.α-ketoglutarate dehydrogenese (citric acid cycle)
3.Transketolase dependent on TPP (hexose monophosphate shunt)
4.The branch chain α-keto acid dehydrogenase (decarboxylase) request
TPP [in catalyses of axidative decarboxylation of branched chain
amino acids: vali, leucin, isoleucin] to the respective keto acids.
5.TPP plays an important role in the transmission of nerve impulse.
Vitamin B1 cocarboxylase: thiamine pyrophosphat
(TPP) – associated with carbohydrate
metabolism

Pyruvate
dehydrogenase

α-ketoglutarate
dehydrogenase

Transketolase
 Vitamin B2 (riboflavin) I

Riboflavin contain 6,7-dimethyl

isoalloxazine (a heterocyclic 3 ring
structure) attached to D-ribitol by a
nitrogen atom. Ribitol is an open chain
form of sugar ribose with the aldehyde
group (CHO) reduced to alcohol (CH2OH).
 Vitamin B2 (riboflavin) –
flavin mononucleotide (FMD)
flavin adenin dinucleotide (FAD)
are two coenzymes forms
take part in redox reactions which are
responsible for energy production
Enzymes that use flavin coenzymes are called
flavoproteins
The functional unit of both the coenzymes is
isoalloxasine ring which serves as an acceptor of two
hydrogen atoms (with electrons). FMD and FAD
undergo identical reversible reactions forming
FMNH2 of FADH2.
Vitamin (B3) niacine (nicotinamide) vitamin PP

Pellagra preventive (PP) factor of

Goldberg (identified by him).
The coenzymes of niacin (NAD+ and NADP+) can
be synthesized by essencial amino acid, tryptophan
 Vitamin B3 (PP)
NAD (nicotinamide adenine dinucleotide)

Vi
t
Vitamin B5 (pantotenate)
Vitamin B6 (pyridoxine)i

Pyridine derivatives:
Pyridoxine
Pyridoxal
Pyridoxamine
Vitamin B6 (pyridoxine)ii

Piridoxal phosphat the coenzyme

which takes part in
transaminations, decarboxylation,
deamination, transsulfuration,
condensation
 Vitamin C
(Ascorbinic acid)

Is a hexose derivative
and closely
resembles
monosaccharides.
Vitamin C [biochemical function]i

1.Collagen formation (plays the role of coenzyme in

hydroxylation of proline and lysine while protocollagen is converted
to collagen [i.e. post-translational modification]; the hydroxylation
reaction is catalysed by lysyl hydroxylase (for lysine) and prolyl
hydroxylase (for proline). This reaction is dependent on vitamin C
molecular oxygen and α-ketoglutarate. Hydroxyproline and
hydroxylisine are essencial for the collagen cross-lincing and the
strength of the fiber. In this way, vitamin C is necessary form
maintenance of notmal connective tissue and wound healing process.
2.Bone formation (bone tissue possess an organic matrix,
collagen and the inorganic calcium, phosphate etc.)
3.Iron hemoglobine metabolism (enhances iron
absorption by keeping it in the ferros form – due to reduction property
of vitamin C. It helps in the formation of ferritin [storage form of iron]
and
mobilization of iron from ferritin)
 Vitamin C [biochemical function]ii

4.Tryptophan metabolism (vitamin C is essencial for the hydroxylation of tryptophan [enzyme-

hydroxylase] to hydroxytryptophan in the synthesis of serotonin)
5.Tyrosine metabolism (vitamin C is required for the oxidation of p-hydroxy phenylpyruvate
[enzyme
hydroxylase] to homogetisic acid in tyrosine metabolism)
6.Folic acid metabolism (The active form of the vitamin folic acid is tetrahydrofolate [FH ] vitamin 4

C is
needed for the formation of FH4 [enzyme-folic acid reductase]. Further, in association with FH4, ascorbic acid is involved in
the maturation of erythrocytes)
7.Peptide gormone synthesis (many peptide hormones contain carboxyl terminal amide which is
derived
from terminal glycin. Hydroxylation of glycine is carried out by peptidylglycine hydrolase which requires vitamin C)
8.Synthesis of corticosteroid hormones (adrenal gland possesses high levels of ascorbinic
acid, particularly in periods of stress. It is believed that vitamin C is necessary for the hydroxylation reactions in the
synthesis of corticosteroid hormones)
9.Sparing action of other vitamins (strong antioxidant)
10.Immunological function (in synthesis of immunoglobulins)
11.Preventive action on cataract (reduces the risk of cataract)
 Para aminobenzoic acid (PABA)

Regarded as a vitamin
in another vitamin
(in folic acid)
 Lipids

The general rule of shorthand notation representing

fatty acid is to show the number of carbon atoms
first, followed by number of double bonds and
finally the (carbon) position of double bonds,
starting from the carboxyl end.
[saturated: palmic acid as
16:0; oleic acid as 18:1; 9;
arachidonic acid as 20:4; 5, 8, 11, 14]
 Lipids (conventional
names)

There are other convention of representing the

double
bond by writing Δ.
Δ9 indicates that the double bond is between 9 and 10
carbon of fatty acids.
ω9 – represents the double bond position (9 and
10) from the ω end.
Lipids (table of main)
 Some important fatty
acidsSuturated fatty acids
Acetic acid [etanolic acid] 2:0 CH3COOH
Propionic acid [n-Propanolic acid] 3:0 CH3CH2COOH
Butyric acid [n-Butanolic acid] 4:0 CH3(CH2)2COOH
Valeric acid [n-Pentanoic acid] 5:0 CH3(CH2)3COOH
Capronic acid [n-Hexanoic acid] 6:0 CH3(CH2)4COOH
Caprylic acid [n-Octanoic acid] 8:0 CH3(CH2)6COOH
Capric acid [n-Decanoic acid] 10:0 CH3(CH2)8COOH
Lauric acid [n-Dodecanoic acid] 12:0 CH3(CH2)10COOH
Myristic acid [n-Tetradecanoic acid] 14:0
CH3(CH2)12COOH Palmitic acid [n-Hexadecanoic acid] 16:0
CH3(CH2)14COOH Stearic acid [n-Octadecanoic acid] 18:0
CH3(CH2)16COOH Arachidonic acid [n-Eicosanoic acid] 20:0
CH3(CH2)18COOH Behenic acid [n-Docosanoic acid] 22:0
 Unsaturated fatty acids

Palmitoleic acid [cis-9-Hexadecienoic acid]

16:1;9 CH3(CH2)5=CH(CH2)7COOH
Oleic acid [cis-9-Octadecienoic acid]
18:1;9 CH3(CH2)7=CH(CH2)7COOH
Linoleic acid [all cis, cis-9,12-Octadecadienoic acid]
18:1,9,12 CH3(CH2)4=CHCH2CH=CH(CH2)7COOH
Arachidonic acid [all cis, cis-5,8,11,14-Eicosatetranoic
acid]
20: 5,8,11,14 CH3(CH2)4=CHCH2CH=CH(CH2)7COOH
 Isomerism of fatty acids
Usually fatty acids exhibit
geometric isomerism
depending on the orientation of groups
around the double bond axis.

Most of the natural occurring unsaturated fatty acids exist as CIS

forms.

CIS isomers are less stable than TRANS isomers.

 Essential fatty acids

Fatty acids that cannot be synthesized by the body and, therefore,

must be supplied in the diet – are known as
essential fatty acids [EFA].
Chemically, they are polyunsaturated fatty acids

Linoleic acid and linolenic acid

are essential since humans lack the enzymes that can introduce
double bonds beyond carbons 9 and 10.

The deficiency of EFA results in phrynoderma and toad skin,

characterized by the presence of horny eruptions on the posterior
and lateral parts of limbs, on the back and buttocks, loss of hair and
poor wound healing.
Ionized form of fatty acids (Palmitate, Oleate)
Triacylglycerols (triacylglicerides, acylglycerols) are
the esters of glycerol with fatty acids.

Are abundant group of lipids that primarily function

as
fuel reserves of animals.

Fats primarily occur in adipose tissue.

Triacylglycerols (triacylglicerides, acylglycerols) are
presented by
monoacylglycerol
s diacylglycerols
triacylglycerols
 Simple triacylglycerols Mixed triacylglycerols

Simple triacylglycerols contains the same type of fatty

acid residue at all three carbons.

Mixed triacylglycerols are more common. They

contain 2 or 3 different types of fatty acid
residue.
In general, fatty acid attached to C1 is saturated, than
attached to C2 is unsaturated while that on C3 can be
either.
Triacylglycerols are named according to placement
 Properties of triacylglycerols

-hydrolysis (catalysed by lipases)

-saponification (hydrolysis by alkali [NaOH]
produces
glycerol and soaps)
-rancidity (deterioration of fats and oils resulting in an
unpleasent taste) substances which can prevent the occurrence
of oxidative rancidity are known as antioxidants
[tocopherols (vitamin E), hydroquinone, gallic acid, α-naphtol;
propyl gallat, butylated hydroxyanisole (BHA), butylated
hydroxytoluene (BHT) – used in food preservation]

In the living cells, lipids undergo oxidation to produce

 Tests to check purity of fats and oils
-iodine number grams [number] of iodine absorbed by
100 grams of fat – is useful to know the relative unsaturation of fats, and is
directly proportional to the content of unsaturated bonds in fatty acids
-saponification number – it is difined as the mg
[number] of KOH required to hydrolyse (saponify) ome
gram of fat or oil. It is a measure of the average molecular
size of the fatty acids present. The value is higher for fats containing short
chain fatty acids
-Reichert-Meissl (RM) number – it is defined as
number of ml 0.1 KOH required to completely neutralize
the soluble volatile fatty acids distilled from 5grams of
fat. RM – useful in testing the purity of butter since it contais a good concentration of valatile fatty acids
(i.e. butiric acid, caproic acid and caprylic acid) – this is in contrast to other fats/oils which have a neglible
amount of volatile fatty acids – adulteration of butter can be tested (if it is decrease).
 Phospholipids (phosphoglycerides)
compound lipids containing phosphoric acid, in
addition to fatty acids, nitrogenous base and
alcohol.
There are two classes of phospholipids:
-(A) glycerophospholipids (phosphoglycerides)
-(B) sphingophospholipides (sphingomyelins)

Principal structure
of phospholipids
(phosphoglyceride)
Phosphatidate (diacylglycerol 3-phosphate)
 -(A) glycerophospholipids (phosphoglycerides)1
[contain glycerol and alcohol]

-consists of glycerol 3-phosphate esterified at its C1

and C2 with fatty acids. Usually, C1 contains a
saturated fatty acid, while C2 contains an unsaturated
fatty acid
 Glycerophospholipids (phosphoglycerides)
They consist of glycerol 3-phosphate esteriffied its C1 and C2 with fatty
acids.
Usually C1 contains a saturated fatty acid
while C2 contains an unsaturated fatty acid.

1.Phosphatidic acid
2.Lecitins (phosphatidylcholin)[dipalmitol lecitin;
lysolecitin]
3.Cephalins (phosphatidylethanolamine)
4.Phosphatidylinositol
5. Phosphatidylserin
e 6.Plasmalogens
7.Cardiolipins
1.Phosphatidic acid glycerophospholipids (phosphoglycerides)1

-phosphatidic acid – simplest phospholipid, does not occur in

good concentration in the tissues – basically it is an
intermediate in the synthesis of triacylglycerols and
phospholipids
Other glycerophospholipids containing different nitrogeneous bases or other groups
 2.Lecitins (phosphatidylcholin)[dipalmitol lecitin;
lysolecitin] glycerophospholipids (phosphoglycerides)2

-lecithins (phosphatidiylecholine) – [λεκιθος – agg yolk]

– storage form of body’s choline [dipalmitoyl lecithin – in
lungs; lysolecithin – is formed by removal of fatty acid either
at C1 or C2 of lecithin]
 a phosphatidylcholine (lecine)
[1-palmitoyl-2-oleoil-phosphatidyl choline] and a space-filling model
 3.Cephalins (phosphatidylethanolamine)
glycerophospholipids (phosphoglycerides)3

-cephalins (phosphatidylethanolamine) – ethanolamine

is
the nitrogenous base present; lecitine and cephaline differ with regard
to the base
 4.Phosphatidylinositol glycerophospholipids
(phosphoglycerides)4

-phosphatidylinosotol – important component of cell

membranes
– stereoisomer myo-inositol is attached to phosphatidic acid.
5. Phosphatidylserine glycerophospholipids (phosphoglycerides)5

-phosphatidylserine – amino acid serin is present in

it
 6.Plasmalogens glycerophospholipids (phosphoglycerides)6

-plasmalogens – fatty acid is attached by an ether linkage at C1 of

glycerol in the glycerophospholipids.
(choline, inositol, serin may substitute ethanolamine in plasmalogens)
 7.Cardiolipins glycerophospholipids (phosphoglycerides)7

-cardiolipin – first isolated from heart muscle – consists of two

molecules of phosphatidic acid held by an additional glycero
through phoshate group
 Components of phosphatidyls
(serine, ethanolamine, choline, glycerol, inositol)
 Phoshatidyls (serine, ethanolamine, choline,
inositol,cardiolipin [diphosphatidil glycerol])
 -(B) sphingophospholipides (sphingomyelins)1
[do not contain glycerol, but contain sphingosine and amino alcohol which are
attached by an amide linkage to a fatty acid]

-sphingosine
-cersamide
-sphingophospholipides (sphingomyelins)1 (space-
filling model of molecule)
 Sphingophospholipides (sphingomyelins)
contains amino alcohol

-ceramide – containing 30-carbon fatty acid – is

a component of skin
ceramide (acts as a second messenger – signaling
molecile – which can regulate programmed cell
death [apoptosis])
 Function of phospholipids

-they are forming the structural componentsbof mambranes and regulate

membrane permeability;
-in the mitochondria (lecithins, cephalins and cardiolipins) maintain the conformation
of electron transport chain components;
-participate in the absorbtion of fat from intestine;
-are essential for the synthesis of different lipoproteins (participate in the transport
of lipids);
-are regarded as lipotropic factors in liver preventing accumulation of fat in it
(preventing fatty liver);
-arachidonic acid (as unsaturated fatty acid liberated from phospholipids) serves as a
precursor for the synthesis of eicosanoids (prostaglandins, prostaciclins,
thromboxans etc.)
-participate in the reverse cholesterol transport and thus help in the removal of
cholesterol from the body;
-phospholipids act as surfactants (agents lowering surface tension) [in
respiratory distress syndrome];
-cephalins are important lipids participate in blood clotting;
-phosphatidylinositol is the source of secondary messengers (inositol triphosphate
and diacylglycerol are involved in the action of some hormones
 Glycolipids (contain a ceramide – sphingosine
attached to fatty acid)

Glycolipids – (glycosphignolipids) – important constituents of cell

membraine and nervous tissue (particulary in the brain).
Cerebrosides are the simpest form of glycolipids. They contain
ceramide (sphignosine attached to a fatty acid) and one or more sugars.
Gangliosides – predominantly found in ganglions – are the most
complex form of glycosphignolipids. They are the derivatives of
cerebrosides and contain one or more molecules of N-acetylneuramatic
acid (NANA), the most important sialic acid.
The most important gangliosides present in the brain are GM1, GM2,
GD, and GT (G represents ganglioside while M, D and T indicate mono-
di- or tri- sialic acid residues) and number denotes the carbohydrate
sequence attached to the ceramide
Lipoproteins (complexes of lipids with proteins)

Lipoproteins – are molecular complexes of lipids with

proteins.
They are the transport vehicles for lipids in the
circulation.
There are five types of lipoproteins, namely:
-chylomicrons
-very low density lipoproteins (VLDL)
-low density lipoproteins (LDL)
-high density lipoproteins (HDL)
-free fatty acid-albumin complexes
 Steroids
Steroids are the compounds containing a cyclic
steroid nucleus (or ring) namly
cyclopentanperhydrophenantren [CPPP]
It consists of a phenanthrene nucleus (rings A, B and
C) to which a cyclopentane ring (D) is attached
 Cholesterol (χολε-bile) [C27H46O]
Exclusively found in animals, is the most abundant animal sterol.
Was first isolated from bile.
Cholesterol literally means ‘solid alcohol from bile’
It has one hydroxyl group at C3 and
double bond between C5 and C6.
An 8 carbon aliphatic side chain is attachanded to C17,
it also contains a total 5 methyl groups (C18, C19, C21, C26, C27)
 Cholesterol (main properties and reactions)
Cholesterol is a yellowish crystalline solid, insoluble in water but
soluble in organic solvents (chloroform, bebzene, ether etc.).

Salkowski’s test
Liebermann-Burchard reaction
Zak’s test
are used for qualitative identification and
quantitative estimation

Due to poor conduction of heat and electricity (it has a high

dielectric constant) cholesterol is present in abundance in nervous
tissues – it appears that it plays an insulating cover for transmission
of electrical impulses in the nervous tissue.
It is precursor in synthesis of bile acids, hormones (sex and
cortical) and vitamin D.
 Ergosterol

Occur in plants, also found as a structural constituent of membranes in

yeast and fungi – is an important precursor for vitamin D. when rxposed
to light, the B ring of ergosterol opens and it is converted to
ergocalciferol, a compound containing vitamin D acivity.
Amphipatic lipids in the formation of
micelle and lipid bilayer
Per definition, - lipids are insoluble in water
(hydrophobic). This primary due to the prebolinant
presence of hydrocarbon groups. However, some of the
lipids possess polar of hydrophilic groups which tend to
be soluble in water. Molecules which contain both
hydrophobic and hydrophilic groups are known as
amphipatic (greek αμφι – both; παϑος – passion)
β-oxidation of fatty acids 1
(whole)
β-oxidation of fatty acids (I phase) activation
β-oxidation of fatty acids (II phase)
fatty acids acyls transport (through membrane)
into
mitochondria (second phase) Transport
β-oxidation of fatty acids (III phase)
Beta oxidation
oxidation
hydration
oxidation
cleavage
Thank You for attention…