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.
⊗ 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
vitamins and vitamin C)
absorption directly into the blood
transport travel without carriers
storage circulate in the water-filled
parts of the body
excretion kidneys remove excess in
urine
toxicity not likely to reach toxic
levels when consumes from
supplements
dosage frequency needed in frequent doses
relationship to function as coenzymes
coenzymes
Fat-soluble Vitamins
(vitamiins A, D, E, and K)
First enter into the lymph system
Many require protein carriers
Found in the cells associated
with fat
Tend to remain in fat-storage
sites
Likely to reach toxic levels when
consumed from supplements
Needed in periodic doses
Do not function as 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.
⊗ 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.

⊗ 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 Vitamin D3 is found in

of plant origin foods 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).
⊗ 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.