CHEMISTRY OF MINERALS - II

Dr. Sudipto Shahid

 Trace Elements

• Trace elements (or trace metals) are minerals present in living

tissues in small amounts. 
• Some of them are known to be nutritionally essential, others may be
essential (although the evidence is only suggestive or incomplete),
and the remainder are considered to be nonessential. 
• Trace elements function primarily as catalysts in enzyme systems;
some metallic ions, such as iron and copper, participate in oxidation-
reduction reactions in energy metabolism.
• All trace elements are toxic if consumed at sufficiently high levels for
long enough periods. The difference between toxic intakes and
optimal intakes to meet physiological needs for essential trace
elements is great for some elements but is much smaller for others.
 IRON (Fe2+ and Fe3+)

• Iron is the most abundant trace metal in the human body. Iron (as
the ferrous ion, Fe2+) is a critical micronutrient with a major role in
the transport of oxygen.
• Iron is the functional center of the heme moiety found in each of
the protein subunit of hemoglobin. The function of Fe2+ is to
coordinate the oxygen molecule into heme of hemoglobin so that
it can be transported from the lungs to the tissues. 
• Aside from its role in oxygen transport, iron is critical to the
overall process of oxidative phosphorylation where it is also
found in the heme of cytochromes and in the Fe-S (iron-sulfur)
centers of the various complex of oxidative phosphorylation. 
 IRON (Fe2+ and Fe3+)
• Iron is the only metal in the human body that is toxic if allowed to
remain free in the plasma or the fluid compartments of cells. The
toxicity of free iron is related to its ability to rapidly generate the highly
toxic hydroxyl free radical (HO--) via the Fenton reaction. For this
reason there are extremely tight controls on overall iron homeostasis.
• Several Iron-Dependent Enzymes
Enzyme Gene Function
Protein encoded by ACO1 functions in the iron-mediated
ACO1, control of translation of the H-ferritin, L-ferritinn,
Aconitases transferrin receptor, DMTI, ferroportin, ALAS2, and ACO2
ACO2 mRNAs; the ACO2 encoded protein is involved in the TCA
cycle.
Primary reaction is to detoxify the reactive oxygen species
Catalase CAT (ROS) hydrogen peroxide (H2O2) to water; can also oxidize
certain alcohols to corresponding aldehydes
 IRON (Fe2+ & Fe3+)
Several Iron-Dependent Enzymes
Enzyme Gene Function
Belong to medium-chain dehydrogenase/reductase (MDR)
Alcohol 7 superfamily; catalyze the oxidation of various alcohols to
dehydroge different their corresponding aldehydes; important in
nases genes the detoxification/metabolism of ethanol.

Multiple
subunits Multisubunit component of oxidative
includin phosphorylation Complex III; contains two
Cytochrom g the Fe- cytochromes b (b-562 and b-566), cytochrome c1, and the
e c reducta S protein
se encoded Fe-S protein which is called the Rieske Fe-S protein after
by the its discoverer J.S. Rieske; official name of this enzyme
UQCRFS complex is ubiquinol-cytochrome c reductase
1 gene
 IRON (Fe2+ & Fe3+)
Several Iron-Dependent Enzymes

Enzyme Gene Function

All three lipoxygenases (5-LOX, 12-LOX, and 15-LOX) are
Lipoxygen ALOX5,
ALOX12, involved in arachidonic acid oxidation during the
ases ALOX15 synthesis of the leukotrienes and the lipoxins.

Official name for these enzymes is procollagen-lysine, 2-

oxoglutarate 5-dioxygenase; PLOD1 is the major
procollagen lysine hydroxylating enzyme; all 3 enzymes
PLOD1, function as homodimers; PLOD2 and PLOD3 carry out
Lysyl
PLOD2,
hydroxylases
PLOD3 hydroxylations in collagen-like proteins; mutations in
PLOD1 are associated with Ehlers-Danlos syndrome
(EDS) type VI, mutations in PLOD2 or PLOD3 are
associated with EDS type VIB.
 IRON (Fe 2+ & Fe3+)

• Recommended daily allowance is 10-20mgs. Sources are meat, fish,

eggs, cereals like wheat & Teff, green leafy vegetables. Milk is
deficient in Iron.
• Absorption is through intestinal mucosa.
• Requires acidic pH of stomach. Ascorbic acid and Ceruloplasmin
promotes absorption.
• Functions: It combines with intracellular binding protein
Apoferritin to ferritin. Almost 300 ferric ions can bind to one
molecule of apoferritin.
• For transport, free iron binds to Apo transferrin, in blood to form
transferrin.It is the major transport form of iron. It also prevents
toxicity of free iron.
 Functions IRON (Fe 2+ & Fe3+)

• Excessive binding of iron causes denaturation of ferritin molecule.

It undergoes aggregation, to form hemosiderin. Mobilization of
iron from hemosiderin is very slow. Thus there is accumulation of
hemosiderin, the condition is called hemosiderosis.
• Massive deposits of hemosiderin in tissues lead to
hemachromatosis. If this takes place in liver, it causes cirrhosis.
• In pancreas, it damages β cells, result in Bronze diabetes. The skin
of the patient has bronze coloration. Oxidative damage to cardiac
muscle is a biggest concern.
• Iron is stored in liver, spleen and bone marrow.
 Homeostasis of Iron in blood

Iron stores ferritin

hemosiderin

Digestion Phagocytes,
Absorption Hemoglobin
Excretion degradation

Blood Iron

Bone marrow, Loss due to bleeding,

Hemoglobin cell death
Synthesis
Enzyme, cofactor
respiration
 Causes of iron deficiency:

-- Storage depletion
– Reduced dietary intake.
– Malnutrition
– Hemolysis
– Children who are on milk diet only are prone to iron deficiency.
– Chronic bleeding, irregular menstrual cycles
– Peptic ulcer, piles
– Hook worm infection
– Repeated malarial infections.
• Deficiency leads to Iron deficiency anaemia or hypochromic
microcytic anaemia.
• It is associated with low hemoglobin and ferritin.
 Copper

• Humans contain around 100 mgs of copper.

• Liver, brain, kidney and heart are rich in copper.
• Free copper is 4%, 96 % is
• Sources: cereals, legumes, raisins, nuts etc bound to Ceruloplasmin
in body.
• Functions: Copper is involved in the formation of red bloods cells,
the synthesis of hemoglobin, and the formation of bone.
• Additional functions of copper are energy production, wound
healing, taste sensation, skin and hair color.
 Functions of Copper

• Copper is also involved in the proper processing of collagen and

elastin via the action of the extracellular matrix-associated enzyme,
lysyl oxidase.
– Thus, copper is critical to the proper production of connective
tissue.
• Cofactor of enzymes like cytochrome oxidase, dopamine
decarboxylase, tyrosinase, Cyt.C oxidase and superoxide dismutase
and monoamine oxidases are dependant on copper. Tyrosyl oxidase is
important for collagen metabolism.
 Functions of Copper

• Ceruloplasmin (serum ferroxidase) catalyses Fe++ to Fe+++, a pre

requisite for the incorporation of iron into transferrin.

• Ceruloplasmin promotes iron absorption.

• Copper deficiency:
– Causes anaemia.(Microcytic,normochromic anemia)
– Failure of melanin formation because tyrosine oxidase becomes
inactive.
 Clinical manifestation of Copper

• Menke’s disease or Kinky hair syndrome:

• It is fatal sex linked recessive disorder in which there is cerebral
and cerebellar degeneration, connective tissue abnormalities and
kinky hair.
– Both serum [Copper] and [Ceruloplasmin] is low.
– Absorption of copper from the intestine is grossly impaired, but
treatment with parentral copper has not proved successful.
– It is X- linked disorder. Patient has normal absorption of iron but
transport across the serosal aspect of mucosal membrane is
defective. Patient suffers from mental retardation.
 Clinical manifestation of Copper

• Wilson’s disease: It is an Autosomal, recessive disorder. There is a

decrease in the biliary excretion of copper. Blood and tissue copper is
high in these patients. It leads to retention of copper, followed by hepato-
lenticular degeneration.
• However, Ceruloplasmin synthesis is incomplete in the liver. Patient
suffers from progressive hepatic cirrhosis and finally liver failure.

• There is dysfunction of lenticular region of brain

• Defective tubular reabsorption in kidney leads to aminoacidurias.
• Copper deposition in the eye, as golden brown or green ring around the cornea.
• Patients are treated with Pencillamine, which binds to tissue copper and
mobilizes it.
 Magnesium

• It is an intracellular ion, essential for life.

• Maximum concentration is found in bones, little in Extra-cellular
fluid (ECF) and soft tissues.
• 2/3 in blood is in ionic form, rest is bound to protein.
• Absorption: It is absorbed from the small bowel.
• Excretion: It is excreted through feces, urine and sweat.
• Sources: Widely distributed in vegetables, chlorophyll, cereals,
beans, potatoes, cheese and animal tissues.
 Functions of Magnesium

• Functions:
– Role in enzyme action. It is a cofactor for peptidases,
ribonucleases, glycolytic enzymes etc.
– Its action is similar to that of calcium in neuromuscular
irritability.
– High levels depress nerve conduction, low levels may cause
Tetany.
– Major part is found in bones. In teeth, it is present as dentin and
enamel.
– Magnesium deficiency occurs rarely in man.
 IODINE

• Iodine is an essential trace element to many species, including

humans. Iodine is believed to be the heaviest element required by
humans.
• Iodine helps make thyroid hormones, which help keep cells and
the metabolic rate (the speed at which chemical reactions take
place in the body) healthy.
• Sources of iodine include:
– sea fish
– shellfish
• Iodine can also be found in plant foods, such as cereals and grains,
but the levels vary depending on the amount of iodine in the soil
where the plants are grown.
 IODINE
• Absorption: It is absorbed from small intestines and transported as
protein complex in plasma.
• Adults need 0.14mg of iodine a day.
• Iodine as iodide is taken up by the thyroid gland, gastric mucosa,
salivary glands and mammary glands in pregnant and breast-feeding
women.
• Function: Iodine is a component of the thyroid hormones and a
strong antioxidant with electric potential.
• In the thyrocytes, the thyroid hormones biosynthesis is carried out by
iodization of tyrosine to T3 and T4.
• Deficiency: The consequences of iodine deficiency are endemic goiter,
irreversible brain damage, cretinism, impaired thyroid function and
thyroid, gastric and mammary glands cancers.
 ZINC

• Zinc is an important trace mineral that people need to stay

healthy. Of the trace minerals, this element is second only
to iron in its concentration in the body
• Sources: liver, milk, fish, dairy products, cereals, legumes, pulses,
oil seeds, yeast and spinach etc.
• Absorption: It is absorbed in duodenum and ileum. Absorption of
Zinc from the intestine appear to be controlled in a manner similar
to Iron.
• It is transported bound to a protein (α2-macroglobulin and
transferrin).
• Diets rich in calcium, phosphates interfere with Zn absorption.
 Functions of ZINC

• Excretion: It is excreted in urine and feces. urinary excretion is fairly

constant at 10 μmol/day.
• Daily Requirements: 15-20mgs for adult, 3-15mgs for infants and
children.
• Functions: Zinc is found in cells throughout the body. It is needed for
the body's defensive (immune) system to properly work. It plays a role
in cell division, cell growth, wound healing, and the breakdown
of carbohydrates.
• Zinc is also needed for the senses of smell and taste. During pregnancy,
infancy, and childhood the body needs zinc to grow and develop
properly. Zinc also enhances the action of insulin.
 Functions of ZINC

Zinc is important for the activity of a number of enzymes like-

– Carbonic anhydrase
– Alkaline phosphatase
– Alchol dehydrogenase
– Porphobilinogn synthase
– Leucine aminopeptidase
– Carboxy peptidase
– Aldolase in glycolysis
DNA, RNA polymerases as zinc has crucial role in DNA.
– Release of vitamin A from liver requires Zinc. Retenene reductase
(zinc enzyme)
 Functions of ZINC

• Expert review on zinc supplements showed that:

• When taken for at least 5 months, zinc may reduce your risk of
becoming sick with the common cold.
• Starting to take zinc supplements within 24 hours after cold symptoms
begin may reduce how long the symptoms last and make the
symptoms less severe. However, supplementation beyond the RDA is
not recommended at this time.
• Symptoms of zinc deficiency include:
– Frequent infections
– Hypogonadism in males
– Loss of hair
– Poor appetite
 Clinicalmanifestation
Clinical manifestationofofSodium
ZINC

• Symptoms of zinc deficiency include:

– Problems with the sense of taste
– Problems with the sense of smell
– Skin sores
– Slow growth
– Trouble seeing in the dark
– Wounds that take a long time to heal
• Zinc supplements taken in large amounts may cause diarrhea, abdominal cramps,
and vomiting. These symptoms most often appear within 3 to 10 hours of
swallowing the supplements. The symptoms go away within a short period of time
after stopping the supplements. An excess intake of zinc can lead to copper or iron
deficiency.
• People who use nasal sprays and gels that contain zinc may have side effects, such
as losing their sense of smell.
 SELENIUM

• Selenium is a mineral found in the soil. Selenium naturally appears

in water and some foods. While people only need a very small
amount, selenium plays a key role in the metabolism.
• Sources: Selenium is rich in liver, kidney, finger nails. Usually plant
products are good sources than animal based diet.
• Absorption: It is absorbed from duodenum, transported as
selenomethionine. It forms a complex with plasma proteins for
transport. In tissues, free selenium is released.
• Excretion: It is excreted in urine.
• Daily requirements: RDA 50-100 μg Adult; 20-120μg Children
 Functions of SELENIUM
• Glutathione peroxidase is a selenium dependent enzyme. The
enzyme has a role in oxidative damage by free radicals. The
enzyme is critically important for the membrane stability of Red
blood cells.
Selenium has sparing action on vitamin E, by three ways.
– It promotes digestion, absorption of lipids and vitamin E.
– It is a part of glutathione peroxidase, prevents peroxidation of
PUFA in the membranes.
– This in turn reduces the requirement of vitamin E.
• It helps in the retention of vitamin E in the blood.
• It is a cofactor for an enzyme involved in the synthesis of thyroid
hormone.
 Functions of SELENIUM
Deficiency of selenium:
– Liver cirrhosis
– Pancreatic degeneration
– Myopathy, infertility
– Failure of growth
• Toxicity:
Selenium toxicity is called Selenosis
Toxic dose is 900micro gram/day
It is present in metal polishes and anti-rust compounds
The Toxicity symptoms are Hair loss,failing of nails, diarrhea,weight loss
and gaslicky odour in breath(due to the presence of dimethyl selenide in
expired air).
• Halogenated aromatic hydrocarbons are useful in the treatment of
Selenosis.
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