UNIT IIl: Chemistry of food biomolecules: Vitamins

Water-soluble and fat-soluble vitamins; loss of vitamins during storage and processing of
foods.

Vitamins, are organic compounds required in very small quantities for a variety of
biochemical functions and which generally cannot be synthesized in the body and therefore
must be supplied in the diet. This definition clearly distinguishes vitamins from inorganic ions
which are also essential for life. Further, unlike the macronutricnts - carbohydrates, proteins
and fats - which are required in large amounts, vitamins are needed in only minute amounts.
Apart from some exceptions, allanimal species require the major vitamins preformed in the
diet due to inability to synthesize them from other food constituents. However, in some
instances, certain precursors present in the diet are sufficient since these precursors can be
converted to the vitamins in the body. One good example of this is the pigment B-carotene is
converted to vitamin A in the body.
Allthe known vitamins can be classified into two groups, depending on their solubility. Tlhese
are the water-soluble vitamins and the fat-soluble vitamins. The former group comprises of the
B
group vitamins and vitamin C, whereas the fat-soluble group includes vitamins A, D, Eand
K. Most of the water-soluble vitamins bave well identified coenzyme functions. The fat-soluble
vitamins, on the other hand, are not known to have any such properties
Classification of Vitamins
Vitamins widely vary from each other fromn the structural point of view. Conventionally, they
are classified on the basis of their solubility in water or fat. Accordingly, they are classified as:
Water-soluble vitamnins, which include thiamine (vitamin Bl), riboflavin (vitamin B2), niacin
and nicotinamide (vitamin B3), pantothenic acid (vitamin B5), pyridoxine and related
compounds (vitamin B6), cyanocobalamin and related compounds (vitamin B12), ascorbic acid
(vitamin C), biotin (vitamin H) and folic acid (vitamin M).
Fat-soluble vitamins, which include retinol (vitamin A), cholecalciferol (vitamin D),
tocopherols (vitamin E) and phylloquinone and related compounds (vitamin K).

FAT SOLUBLE VITAMINS

These vitamins are non-polar, hydroplhobic molecules which are not soluble in water but
readily dissolve in fats. Fat soluble vitamins include vitamin A and carotene (provitamin A),
vitamin D, vitamin E and vitamin K. These are fairly stable and are not destroyed by heat and
are normally not lost in the cooking process. The fat-soluble vitamins are isoprene derivatives
and are absorbed along with the normal fats in human beings. They are transported by
lipoproteins or with the help of other specific binding proteins in the blood. The body is able
to store excess of fat-soluble vitamins in the liver and other fat storage sites and are made
available when one is on a vitamin deficient diet. However, an overdose of these vitamins may
have toxic effects leading to hypervitaminosis. Therefore, addition of fat-soluble vitamins to
the food or taking vitamin supplements must be carefully controlled.
 Vitamin A(retinol)
The retinol fornm functions as a storage form of the vitamin, and can be
converted to and from
its visually active aldehyde form, retinal. All forms of vitamin A have a
beta-ionone ring to
which an isoprenoid chain is attached, called a retinyl group. Both structural features are
essential for vitamin activity.

CH
CH20H

CHa
Retinol
MC CH

CH3
Retinal (etinaldehyde)
CH
COOH

Retinoic Acid
CHa
H3C.
M3C CH3

Bcarotene HaC CHa

CH3

The physico-chemical properties of Vitamin A are as follows:

a) Itis pale yellow almost colourless liquid.
b) It is soluble in fat and fat solvent but insoluble in water.
c) It can withstand cooking temperature 100 Cfor ashort period in absence of oxygen.
d) Fats containing retinol becomes rancid on oxidation which destroys vitamins.
e) On exposure to Sunlight it gets destroyed.
) Oxidation and subsequent destruction of retinol is prevented in the presence of Vitamin E.

Vitamin A occurs only in animal tissues. But many plant tissues contain substances
(precursors) which can be converted to vitamin A in the body. These are the yellow or red
coloured carotenoid pigments found in plans. These include carotene; (a. Band à) and the
related compounds (cryptoxanthin) known as provitamin A.
The active forms of vitamin A are:

retinol having an alcoholic group (CH;OH)

retinal (also called retinaldehyde) having an aldehyde group (CHO), and
retinoic acid having a carboxylic group (COOH).

Dietary Sources
"Only in fish liver oil and foods ofanimal origin such as liver, cggs, milk and fatty fish.
Plant foods contain only carotenoids (the precursor of vitamin A) and include green leafy
vegetables, tomato, carrot, mango and other yellow coloured fruits
SIn Physiologicai Functions
" Maintenance of normal vision
" Building and grOwth of skeletal cells and provides immunity to the
"Dictary retinoids, especially carotenoid compounds have body
been found to suppress
carcinogenesis (development of cancer)
"Both retinoids and carotenoids have anticancer activity. This
again is attributed to the role of
retinoids in cell differentiation.
"ß-carotene is an antioxidant,

Deficiency Diseases
"Night blindness
" In carly stages of vitamin A deficiency, one cannot see well in dim light
" In advanced deficiency, the person cannot see objects in dim light
" cessationof growth and keratinization of the epithelium in various parts of the body, such as
the respiratory, alimentary, reproductive and genitor urinary tracts,
"defects in the teeth,
" disturbances in bone growth

Hyper-vitaminosis
" Mild: nausea, irritability, blurring of vision
"Severe: growth retardation, cnlargement of liverand spleen, hair loss, increased skull pressure

Applications
" Vitamin Adry powder- Viamin Adry powder is used in the (manufacture of dry mixtures)
for which the oily ester concentrates are unsuitable or undesirable. Mainly, they are
incorporated in dry formulations such as (coated tablets and capsules). Even in animal feed
industry, vitamin Adry powder is preferred. The stability of vitamin Ain the dry powder is
increased by matrix coating of the esters with gelatin, thus protecting them from direct
oxidation.

. Water soluble Vitamin A- Water soluble vitamin A is ayellowish green, slightly turbid,
fluorescent liquid of faint characteristic odour. The taste is at first faintly sweet and then bitter.
Water soluble vitamin A is especially suitable for the manufacture of solutions for oral
administration. This preparation contains the palmitate of vitamin A. This ester which
otherwise is only fat soluble, has been rendered miscible with water and aqueous liquids by a
solubilizer. The stabilizer added to the preparation moreover delays possible loss of activity
due to atmospheric oxidation.

lamin D (calciferoi vitamin D2)

Vitamin D is agroup of compounds related to sterols. Sterols are polyaromatic alcohols. This
vilamin occurs in several forms, the two most important are vitamin D2 or ergocalciferol and
vilamin D3 or cholecalciferol. Vitamin D2 produced by the UV irradiation of ergosterol,
of 7
present in yeast and moulds. Vitamin D3 is produced by the UV irradiation
dehvdrocholesterol, present in the skin. The active form of vitamin D is 1, 25 dihydroxy
cholecalciferol (calcitriol).
(cholecalciferol
The maun forms are Vitamin D:(ergocalciferol-plant origin) and vitamin D3 without
powder
animalorigin). Vitamin D2 forms colourless, acicular crystals or a crystalline
chloroform or benzene,
taste and of only faint odour. Vitamin D2 is easily soluble in either
against
ethanol, acetone and fatty oils and insoluble in water. Vitamin D2 is sensitive
atmospheric oxygen. It is not stable either in the presence of oxidizing substances and oxygea
visible
carriers. Moreover, vitamin D2 is destroyed by acids, metal ions as well as UV and
light.

H,C CH

H,C
H,

HO

The physiro-chemical properties of Vitamin D are as follows:

a) They are soluble in fats and fat solvent.
b) They are not destroyed in presence of acid and alkali.
c) They are fairly stable tooxidation.
d) Can withstand cooking temperature 100C and preserving process.
e) More stable than vitamin A.

Dietary Sources
" Vitamin D2 occurs in small amounts in fish liver oils
Vitamin D3 is widely distributed in eggs, milk, butter and cheese but large amounts occur
only in fish liver oils

Physiological Functions
" Essential for bone formation
" Promotes absorption of calcium and phosphorous and deposition in bone
" Involved in the formation of teeth
The principal function of the active form of vitamin D i.e. 1,25
dihydroxycholecalciferol
(calciriol), is to maintain the plasma calcium concentration at desirable level. It achieves this
in three ways. It
iincreases intestinalabsorption of calcium,
reduces excretion of calcium by stimulating resorption in the distal tubules (in
the kidnev).
and
iii mobilizes bone mineral by dissolving calcium deposited in the bone matriy
Deficiency Diseases
bone does not take place
.Calcification (caleium deposition) of and children leading to bowleg, enlargement
of
called rickets in infants
. Result in the discase bones called 'pigeon breast',
osteomalacia in
and deformities of the chest
ankles andwrists
older people.

Hyper-vitaminosis
irritability
"Mild: nausea, weight loss,
growth retardation, kidney damage
"Severe: mental and physical

Applications formulations. For the animal feed

mainly used in the preparation of various drug In many
Vitamin D2 is
dry powder under the name of vitamin D2 is available.
industry, amineral stable with vitamin D serve
and milk products, margarine and vegetable oils fortified
countries, milk
of vitamin.
as a major dietary source

VitaminE (Tocopherols)
derivatives of
group of compounds known as tocopherols which are the
Vitamin E refers to a tocopherols namely a, B. and õ
tocopherols
'tocopherol. Four
a parent compound called as each other in the number and position of methyl
groups
have been isolated. They differ from
tocopherols have two methyl groups, a and ß
attached to the aromatic nucleus. While Band 2respectively. Allof these compounds possess
tocopherols have three and one methyl groups, synthesized
physiological properties, although a-tocopherol which is
comparable
commercially is most potent.

All feature
four tocopherols and four tocotrienols.
Vitamin E exists in eight different forms, hydrogen atom to reduce free radicals
can donate a
achromane ring,with a hydroxyl group that penetration intobiological membranes.
and a hydrophobic side chain that allows for

CH,
HO CH,
CH, CH
CH,
H,C CH,
CH,

and UV
VitaminE has excellent antioxidant properties and is destroyed by oxidising agents
protects vitamins A
light: bowever, it is fairly resistant to heat. As an antioxidant, vitaminE
of
and C. red blood cells and essential fatty acids from destruction. Regular consumption
antioxidant-rich fruits and vegetables is claimed to be associated with lowering risk for heart
disease, cancer and several other diseases, Since dpha tocopherols have the highest binogial
activity, its content is taken for calculating the human requlrements, D-49opheol is mainly
omwdjtcs,
used as an antioxidant in stabilising edible oils, lats and 1al-containing foon
pharmaceut ical preparations and cosmetics.
Physico-chemical properties of vitamin E are as follows:
a) Tocopherols are yellow, oily liquids.
b)They are frecly soluble in fat solvents.
withstand a temperature slyy
c) The compounds are remarkablystable to heat. They can even
100°C.
d) Activity of vitamin E is destroyed in presence of oxidizing agents,
e) Inalkaline medium, tocopherols are destroyed.
)They are, however, stable to acidic medium.
g) When exposed to ultra violet light, the vitamin is destroyed.
h) All these compounds exhibit strong antioxidant properties.
Dietary Sources
natural soures
" Delta tocopherols were isolated from soybean oil as the richest
"Cercal germ oils like wheal germ oil and corn germ oils, soybean oil
"Cottonsced oil contains alpha, beta, and gamma tocopherols

Physiological Functions
" Essential for normal reproduction in several species of animals and also in human beings

Deficiency Diseases
" Reproductive failure
" Liver necrosis (damage)
" Muscular dystrophy, ctc. The cardiac and smooth muscles as well as the skelctal muscles arc
affected.

Hyper-vitaminosis
" Severe: nausea, digestive tract disorders

Applications
DL-u-Tocopherol is mainly used as an antioxidant in stabilizing edible oils and fats and fat
containingfood commodities, pharmaceutical preparations and cosmet ics.

Vitamin K(Menadione - Vitamin K3, oil soluble)

Ifyou get a small cut, bleeding occurs. But very soon withoul even any effort on your pan, the
bleeding stops. This is because a blood clot is formed. Vitamin Kis required for this process
AllVitamin K group members are composed of a methylated naphtoquinone ripe, which is
also known as menadione. Vitamin Ki. phylloquinone, contains four isoprenoid resjdues, in
 composed of
which one is unsaturated, in its side chain. Vitamin Kz, menaquinone, can be
varying numbersof unsaturated isoprenoid residues.
benzene, soluble in
Menadione is a yellow, lustrous, crystalline powder. It is easily soluble in
very sparingly soluble
fats and fatty oils. lt is sparingly soluble in ethanol and chloroformnotandstable in the presence of
Menadione is
in water. Melting point is between 105 and 108°C.
acid as well as of alkalis and substances with alkaline reaction and in the presence of reducing
decompose menadione with brown
agents. Exposure to light and ultraviolet light will
discolouration.

Vitanun KI
(phsllqunone)

Vilam1n K2
(menaquinone)

(menadkne)

Physico-chemical properties of vitamin K are as follows:

a) Highly sensible to light.
b) Fairly stable to heat treatment.
c)They are alkali sensitive.
d) Vitamin K,,is yellow oil, whereas, Vitamin Kz is a yellow ctystalline solid.
e) The natural vitamins K are only soluble in fat solvents.
)Vitamin Kg is slightly soluble in water for not having the long hydrocarbon chain.
Dietary Sources
" Occurs widely inplant foods,especially in leafy vegetables like spinach, cabbage, alfa-alfa
" Almost 50% of the vitamin requirement is derived from intestinal micro-organisms.

Physiological Functions
Essential for blood cloting by increasing the prothrombin levels in blood.
Vitamin Kis requíred for the synthesis of various proteins which are needed for the process of
bloodclolting. The proteins needed for blood cloting are secreted in an inactive form called
precursors. They have to be converted into the active state, following which they help in the
blood cloting process. Vitamin K is required for this conversion. Hence low levels of vitamin
K result in decreased clotting of blood. The mechanism of this action has been most clearly
understood in the ase of one of the proteins (clotting factor) called prothrombin. Prothrombin
is blood clotting lactor |1. Prothrombin is synthesized as an inactive precursor called pre
prothrombin. ThËs is. a protein mo lecule and i contains the amino acid glutamic acid units
(residues) in its polypeptide chain. Conversion of pre prothrombin (inactive) to prothrombin
(active) requires carboxylation (introduction of COOH groups) of some of the glutamate
residues. This 0s catalysed byacarboxylase enzyme which requires vitamin Kfor its activity.

Deficiency Diseases
"Inadequate intake or inadequate intestinal absorption of vitamin K
" lnadequate intestinal absorption canoccur due to discase ofthe liver or diarrhoea
" Deliciency leads to increascd blood cloting time. This may lead to haemorrhage conditions.

Hyper-vitaminosis- No significant consequence reported, however, in severe cases the

liver may get damaged.
Applications- Menadione is used in the preparation of drug formulations and vitamin K
supplementation of feed mixes and infant formula.

WATER SOLUBLE VITMINS

The vitamin Bcomplex comprises the vitamins B1, B2, B6 and B12 as well as the vitamin B
lactors biotin, folic acid, nicotinic acid and its amide as well as pantothenic acid. Besides,
inositol, choline and adenine (vitamin B4) are considered as vitamins of the Bcomplex. In
nature, the active principles of the vitamin Bcomplex mostly occur together.
The water-soluble vitamins may be classified into 3 groups depending on their function:
energy-releasing water-soluble vitamins: Bl, B2, B6, niacin, pantothenic acid and
biotin
hematopoietic water-soluble vitamins: folic acid, vitamin BI2
other water-soluble vitamins: ascorbic acid (vitamin C).

Thiamine (vitamin B,)

Thianine is acolorless organosulfur compound with a chemical formula C1zHiN4OS. Its
structure consists of an aminopyrimidine and a thiazolium ring linked by a methylene bridge.
Pyrimidine and thiazole ring, are the t(wo rings present in the structure of thiamine. The thiazole
is substitutedwith mehyland hydroxyethylside chains.
The chemical name for this water soluble vitamin is 3-[(4-amino-2-methyl-5- pyrimidinyl)
methyl) - 5-(2-hydroxyethy1 )-4-methylthiazolium. The active form in which thiamine
functions in the body, is called thiamine pyrophosphate-TPP (also called thiamine
diphosphate).
 NH,

H,C H,C
OH

The important physico-chemical properties of thiamine are as follows:

substance.
a) Thiamine hvdrochloride is a white, needle-shaped crystalline
characteristic smell of yeast is due
smell like that of yeast. In fact, the
b) It has acharacteristic
sulfurours odour and a bitter
to its content of thiamine. Thiamine has a
soluble in alcohol. This pro perty
c) The compound is readily soluble in water and slightly washing/soaking and other
makes it vulnerable, as thiamine in foods is easily lost during
destruction and thus it is much less stable to
cooking procedures. Moisture greatly accelerates
heat in fresh foods than in dry foods.
but destroved, if heated at 120°C for 30
d) I is stable in acid medium at room temperature
minutes.
medium. It is very sensitive to
c) Thiamine is readily destroyed by heat in neutral or alkaline
alkaline medium. This again is an
alkali and can be even destroyed at room temperature in an
you read through the water
important consideration during cooking procedures. In fact, after most of the vitamins in this
case of
soluble vitamins, you will realize that this is true in the
group.
by controlled oxidation (by
)The compound is converted to an inactive derivatiye-thiochrome
Thiochrome has a strong fluorescence
the action of potassium ferricyanide in alkaline solution).
in UV rays.
into pyrimidine
g) Thiamine, when dissolved in sodium bisulphate solution at pH 5.0 cleaves
the vitamin.
and thiazole. This property is utilized for the chemical estimation of

Dietary Sources
Whole cereals, pulses (legumes), oilsecds, cggs, pork and nuts

Physiological Functions
" Functions in carbohydrate metabolism.
" Free thiamine is readily absorbable by small intestine
"Necessary for nerve function, appetite and normal digestion

Thiamine diphosphate (TDP) is the coenzyne for three multi-enzyme complexes that catalyse
Oxidative decarboxylation (oxidat ion and decarboxylat ion) reactions. These are:
Pyruvate dehydrogenase in carbohydrate metabolism
a-ketoglutarale dehydrogenase in the citric acid cycle
branched-chain keto-acid dehydrogenase in metabolism of branched-chain amino acids
(leucine, isoleucine and valine).