Vitamins

Vitamin is an organic compound, essential in

small amounts for the proper functioning of the
human body, that must be obtained from
dietary sources because the body cannot
synthesize it.
 Vitamins
• Vitamins differ from the major classes of
nutrients in foods in the amount required; for
vitamins, it is microgram to milligram
quantities per day compared with 50-200
grams per day for the major food nutrient
categories.
 Vitamins
• A well-balanced diet usually meets all the
body’s vitamin requirements. However,
supplemental vitamins are often required for
women during pregnancy and for people
recovering from certain illness.
Solubility characteristics divide the vitamins into
two major classes:

Water-soluble vitamins Fat-soluble vitamins

Vitamin C Vitamin A
Thiamin Vitamin D
Riboflavin Vitamin E
Niacin Vitamin K
Pantothenic acid
Vitamin B6
Biotin
Folate
Vitamin B12
 General Properties of Water-soluble vitamins
and Fat-soluble vitamins
Water-soluble Vitamins (B Fat-soluble Vitamins (vitamiins A,
vitamins and vitamin C) D, E, and K)
absorption directly into the blood First enter into the lymph system
transport travel without carriers Many require protein carriers
storage circulate in the water-filled Found in the cells associated with
parts of the body fat
excretion kidneys remove excess in urine Tend to remain in fat-storage sites
toxicity not likely to reach toxic levels Likely to reach toxic levels when
when consumes from consumed from supplements
supplements
dosage frequency needed in frequent doses Needed in periodic doses
relationship to function as coenzymes Do not function as coenzymes
coenzymes
Best known of all vitamins, was first to be structurally characterized (1933), and
the first to be synthesized in the laboratory.
 Vitamin C
• Has the simplest structure of the 13
vitamins, exists in two active forms in the
body: an oxidized form and a reduced
form.

(reduced) (oxidized)
Vitamin C biosynthesis involves L-gulonic acid, an acid derivative
of the monosaccharide L-gulose, L-gulonic acid is changed by
the enzyme lactonase into a cyclic ester; ring closure involves
carbon 1 and 4. An oxidase then introduces a double bond into
the ring, producing L-ascorbic acid.

oxidase
 Vitamin C
• In humans, an intake of 100 mg/day of
vitamin C saturates all body tissues with
the compound. After tissue saturation, all
additional vitamin C is rapidly metabolized
and excreted in the urine.
• The RDA for vitamin C varies from country
to country. Country RDA

Great Britain 30 mg/day

United States 60 mg/day
Canada 60 mg/day
Germany 75 mg/day
 Vitamin C
Important biochemical functions for vitamin C in the
human body include the following:
• Collagen Synthesis – vitamin C functions as a
cosubstrate in the formation of the structural
protein collagen, which makes up much of the skin,
ligaments, and tendons and also serves as the
matrix on which bone and teeth are formed.
 Vitamin C
• General Antioxidant – One way it acts a
general antioxidant is by “recharging” spent
enzymes that contain metal ions.
 Vitamin C
• Synthesis of Neurotransmitter – synthesis of
neurotransmitters dopamine and
norepinephrine from the amino acid
tryosine, and the neurotransmitter
serotonin from the amino acid typtophan
depend on the presence of vitamin C.
All B vitamins serve as precursors for enzyme cofactors.
Vitamin C is NOT an enzyme cofactor precursor.
 Vitamin B
1. Thiamin (vitamin B1)
2. Riboflavin (vitamin B2)
3. Niacin (nicotinic acid, nicotinamide,
vitamin B3)
4. Pantothenic acid (vitamin B5)
5. Vitamin B6 (pyridoxine, pyridoxal,
pyridoxamine)
6. Biotin (vitamin B7)
7. Folate (folic acid, vitamin B9)
8. Vitamin B12 (cobalamin)
• No Vitamin B4 or vitamin B8 entry is found in
the listing. The substance originally identified as
vitamin B4 was later found to adenine, and
vitamin B8 was found to be adenylic acid,
another DNA metabolite. Thus, “vitamins” B4
and B8 dropped out of the system.
 Structural Characteristics of
the B vitamins
• The “active form” for vitamins in the body
is their enzyme cofactor form, to which
they are converted once they obtained
from food through digestion.
 Structural Characteristics of
the B vitamins
• As structural aspects of the various B
vitamins are now considered, emphasis is
given to the chemical modifications that
occur as the “free” vitamins re converted
to enzyme cofactor form(s), that is, to
their active forms in the body.
 Thiamin (Vitamin B1)
• Thiamin (vitamin B1)

free

Coenzyme form
 Thiamin (vitamin B1)

• The name thiamin comes from “thio”, which means

“sulfur” and “amine” which refers to the numerous
amine groups present.
• The coenzyme form of thiamin called thiamine
pyrophosphate (TPP), a molecule in which a
pyrophosphate group (two phosphates bonded to
each other) has been attached to the side chain.
 Thiamin (vitamin B1)

• The coenzyme TPP is needed in step 4

(decarboxylation of an α-keto acid) of the citric acid
cycle and also in the conversion of pyruvate to acetyl
CoA.
 Riboflavin (vitamin B2)
Riboflavin’s structure involves three fused six-membered
rings (two of which contain nitrogen) with the
monosaccharide ribose attached to the middle ring.
 Riboflavin (vitamin B2)

• “yellow vitamin” because of it’s color

• Flavin means “yellow” in Latin

2 important riboflavin-based coenzymes exist

✓ FAD (flavin adenine dinucleotide)
✓ FMN (flavin mononucleotide)

Both coenzymes are involved with oxidation-reduction

reactions.
 Niacin (vitamin B3)
• Niacin occurs in food in 2 different, but
similar forms: nicotinic acid and
nicotinamide.
 Niacin (vitamin B3)

• Nicotinic acid – first described in 1873,

prepared by oxidizing nicotine using nitric
acid; hence the name nicotinic acid.

• Nicotinamide – NAD (nicotinamide adenine

dinucleotide
– NADP+ (nicotinamide adenine
dinucleotide phosphate
 Pantothenic acid (Vitamin B5)

• Pantothenic acid comes from the Greek word

“pantothen,” which means “from
everywhere.” This vitamin is found in almost
every plant and animal tissue.
 Pantothenic acid (Vitamin
B5)
• The structure of pantothenic acid can be
envisioned as an amide formed from the
reaction of β-alanine and pantoic acid
(2,4-dihydroxy-3,3-dimethylbutanoic acid),
a carboxylic acid.
 Pantothenic acid (Vitamin
B5)

• Coenzyme A (CoA) one of the most used of

all vitamin B coenzymes, contains
pantothenic acid as part of it’s structure.
CoA is required in the metabolism of
carbohydrates, lipids, and proteins, where
it is involved in the transfer of acetyl
groups between molecules.
 Vitamin B6 (Pyridoxine, Pyridoxal,
and Pyridoxamine)
• Vitamin B6 is a collective term for three related
compounds:
▪ Pyridoxine – found in foods of plant origin
▪ Pyridoxal and pyridoxamine – found in foods of
animal origin

Vitamin B6 coenzymes participate in reactions where

amino groups are transferred between molecules.
Such transfer occurs repeatedly when protein
molecules are metabolized.
 Biotin (vitamin B7)
• Biotin is unique among the B vitamins in that it can
be obtained in both from dietary intake and also via
biotin-producing bacteria (microbiota, hence the
name biotin) present in the large intestine.
 Biotin (vitamin B7)
• Biotin a fused two-ring system with one ring
containing sulfur and the other ring containing
nitrogen. Attached to the sulfur-containing ring is a
pentanoic acid residue.
 Biotin (vitamin B7)
• “Free biotin is biologically active. However,
its principal active forms involve
coenzymes formed when the carboxyl
group of biotin’s pentanoic acid forms an
amide linkage with lysine present at an
enzyme’s active site.
 Biotin (vitamin B7)

• As a coenzyme, biotin participates in

carboxylation reactions, reactions in
which a carboxyl group is added to a
molecule.

*pyruvate carboxylase is a biotin containing enzyme.

 Folate (Vitamin B9)

• Folate comes from the Latin word “folium,”

which means “leaf.” Dark leafy vegetables are
the best natural source for folate.
 Folate (Vitamin B9)
Consist of three parts: nitrogen containing
double ring system (pteridine, PABA, and
one or more of the amino acid glutamate)
 Folate (Vitamin B9)

When only one glutamate residue is present, the

folate is called folic acid.
 Folate (Vitamin B9)

• In food, about 90% of the folate molecules have

3 or more glutamates present; such molecules
are called polyglutamates.

• The active coenzyme form of folate,

tetrahydrofolate (THF), has only one glutamate,
and four hydrogen atoms have been added to
the double-ring nitrogen system.
 (THF) tetrahydrofolate

THF is needed in methylation reactions, reactions in which one or more

methyl groups are transferred from one molecule to another.
 Vitamin B12 (Cobalamin)
• Only vitamin that contains a metal atom.
free coenzyme
 Vitamin B12 (Cobalamin)
• “free” vitamin B12 and coenzyme vitamin B12
differ only in one attachment to the cobalt atom.
• B12 coenzymes participate in the transfer of
alkyl groups and hydrogen atoms from one
molecule to another.
 Vitamin B12 (Cobalamin)
• Only microorganisms can produce vitamin B12; it
cannot be made by plants, animals, birds, or
humans. Grazing animals acquire vitamin B12 by
ingesting some soil during the grazing process.
Bacteria present in the multi-compartment
stomach of cows and sheep can produce vitamin
B12.
 Vitamin B12 (Cobalamin)
• Humans obtain this vitamin from food of animal
origin or from ready-to-eat breakfast cereals.
In their function as coenzymes, B vitamins usually
do not remain permanently bonded to the
apoenzyme that they are associated with. This
means, they can be repeatedly used by various
enzymes.
 Selected important coenzymes in which B vitamins are present

B Vitamin Coenzymes Groups Transferred

thiamin thiamin pyrophosphate carbon dioxide
(TPP) (carbonyl group
riboflavin flavin mononucleotide hydrogen atoms
(FMN)
flavin adenine
dinucleotide (FAD)
niacin nicotinamide adenine hydrogen atoms
dinucleotide (NAD+)
nicotinamide adenine
dinucleotide phosphate
(NADP+)
 Selected important coenzymes in which B vitamins are present

B Vitamin Coenzymes Groups Transferred

pantothenic acid coenzyme A (CoA) acyl groups
vitamin B6 pyridoxal-5’-phosphate amino groups
(PLP)
pyridoxine-5’-phosphate
(PNP)
pyridoxamine-5’-phosphate
(PMP)
biotin biotin carbon dioxide
(carboxyl group)
folate tetrahydrofolate (THF) one-carbon groups
other than CO2
vitamin B12 methylcobalamin methyl groups,
hydrogen atoms
 Fat-Soluble Vitamins
• The structure of fat-soluble vitamins
involve processes that occur in cell
membranes. The structure of fat-soluble
vitamins are more hydrocarbon-like, with
fewer functional groups than the water-
soluble vitamins.
 Fat-Soluble Vitamins
• Their structures as a whole are nonpolar,
which enhances their solubility in cell
membranes.
 Vitamin A

• Normal dietary intake provides a person with both

performed and precursor forms of vitamin A.

• Forms of Vitamin A:
Performed = retinoids (retinal, retinol, and
retinoic acid)
Precursor = carotenoids
Vitamin A

R= CH2OH (retinol)
R= CHO (retinal)
R= COOH (retinoic acid)
 Vitamin A
• The biochemical activity of retinol exceeds that of
the other two forms.
• The body can synthesize retinol from retinal in a
reaction that is reversible; retinal can also be
converted to retinoic acid in an irreversible
reaction.
 Vitamin A
• Foods derived from animals, including egg yolks
and dairy products, provide vitamin A in the form
of retinyl esters, compounds that are easily
hydrolyzed to retinoids in the human intestine.
 Vitamin A
• Foods of plant origin provide carotenoids.
The major carotenoid with vitamin A
activity is beta-carotene, which is cleaved
to yield two molecules of retinal, which can
be converted to retinol.
 Vitamin A
4 major functions of vitamin A:

1. Vision – retinal combines with protein opsin to form

the visual pigment rhodopsin (participates in the
conversion of light into nerve impulses sent to the
brain.
2. Regulating Cell differentiation - vitamin A (retinoic
acid) binds to receptors; these vitamin A-protein
complexes then bind to regulatory regions of DNA
molecules.
 Vitamin A
4 major functions of vitamin A:

3. Maintenance of the health of epithelial tissues – lack of

vitamin A (retinoic acid) causes such surfaces to become
drier and harder then normal. (mucus-secreting cells).

4. Reproduction and Growth – In men, vitamin A

participates in sperm development. In women, normal
fetal development during pregnancy. Both forms needed
is the retinoic acid.
 Vitamin D
Fatty fish such as
salmon and egg yolks
are good natural
sources of vitamin D.
Fortified with vitamin D
include milk and
margarine.
 Vitamin D
The rest of the body’s
vitamin D supplies are
made within the
body(skin) with the help
of sunlight.
 Vitamin D

Vitamin D2 is found in foods of Vitamin D3 is found in foods

plant origin of animal origin

Structurally, vitamin D2 and D3 are similar, differing only in the hydrocarbon side
chain present In their structures.
Vitamin D
Both the colecalciferol
and ergocalciferol forms
of vitamin D must
undergo two further
hydroxylation steps
before the vit. D becomes
fully functional.
Vitamin D
1st step: addition of –OH
group to carbon 25 (liver)
producing calcidiol

2nd step: -OH group to

carbon 1 (kidney)
producing calcitriol
 Vitamin D
• Vitamin D3 is produced in the skin of
humans and animals by the action of
sunlight (UV light) on its precursor molecule,
the cholesterol derivative 7-
dehydrocholesterol (normal metabolite of
cholesterol found in the skin).
 Vitamin D
• Absorption of light energy induces breakage
of the 9,10-carbon-cabon bond; a
spontaneous isomerization (shifting of
double bonds) the occurs.
Spontaneous
conversion
 Vitamin D
Functions of vitamin D:

• Maintain normal blood levels of calcium ion and

phosphate ion so that bones can absorb these
ions
• Stimulates absorption of these ions from the
gastrointestinal track and aids in their retention
by the kidneys
 Vitamin D
Functions of vitamin D:

• Triggers the deposition of calcium salts into the

organic matrix of bones by activating the
biosynthesis of calcium binding proteins.
 Vitamin E
4 forms of vitamin E: alpha-, beta-, delta-, and
gamma-tocopherol differ from each other
structurally according to which substituents
are present at two positions on an aromatic
ring.

R1 R2
α CH3 CH3
β CH3 H
γ H CH3
δ H H
 Vitamin E
Sources: vegetable oils, margarines, salad dressings,
spinach, broccoli
 Vitamin E
Function:

Antioxidant – prevents other compound from

oxidation by being oxidized itself. Vitamin E is
unique among the vitamins as its antioxidant
activity is the principal biochemical role.
 Vitamin K
Green leafy vegetables such as spinach and cabbage
are rich in Vitamin K. Other vitamins such as peas
and tomatoes, as well as animal tissues including liver,
contains lesser amounts.
 Vitamin K
• The various forms differ structurally in the
length and degree of unsaturation of the
side chain.
• Vitamin K1, is also called phylloquinone,
has a side chain that is predominantly
saturated; only one carbon-carbon bond is
present.
 Vitamin K
Vitamin K2 has several
forms called
menaquinones, various
forms differing in the
length of the side chain.
It has several carbon-
carbon double bond.
 Vitamin K

Vitamin K2 is found in animals and humans

and can be synthesized by bacteria,
including those in the intestinal tract.
 Vitamin K
Function:

1. Essential to the blood clotting process

(essential in the formation of prothrombin and
five other proteins involved in the regulation of
blood clotting.)
2. Also required for the biosynthesis of several
other proteins found in the plasma, bone, and
kidney.