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Minerals

International Mineralogical association approved


the following definition in 1995:
"A mineral is an element or chemical compound
that is normally crystalline and that has been
formed as a result of geological processes.”
Minerals: macro, trace, non-essential trace, &
electrolytes
 Boron  Magnesium
 Calcium  Manganese
 Chlorine  Molybdenum
 Chromium  Phosphorus
 Cobalt  Potassium
 Copper  Selenium
 Fluoride  Sodium
 Iodine  Sulfur
 Iron  Zinc
Macrominerals
• sodium
• chloride
• potassium
• calcium
• phosphorus
• magnesium
• sulfur
Minerals in a 60-kilogram (132-pound) Human Body

MAJOR MINERALS
The major minerals are those present in amounts
larger than 5 g (a teaspoon). A pound is about
454 g; thus only calcium and phosphorus appear
in amounts larger than a pound.

TRACE MINERALS
There are more than a dozen trace minerals,
although only six are shown here.

Amount (g)
SODIUM
• atomic number : 11.
• soft, silvery-white, highly reactive metal
• member of the alkali metals
• one stable isotope : 23Na.
• 1807 : Humphry Davy
• elemental sodium does not occur naturally on
arth, because it quickly oxidizes in air and is
violently reactive with water
• ion is soluble in water
• it is mostly counterbalanced by
the chloride ion sodium chloride
Function
• build up an electrostatic charge on cell
membranes
• regulates blood volume and blood pressure
• osmotic equilibrium and the acid-base
balance
Action potential
CHLORIDE
• Chlorine
– atomic no. : 17
– has highest electron affinity and the third highest
electronegativity of all the elements
– In nature, chlorine is found primarily as
the chloride ion — about 1.9% of the mass of
seawater is chloride ions.
Chloride
• essential nutrient
• fluid and electrolyte balance
• abundant in foods (especially processed)
– part of sodium chloride
• rarely lacking
• dehydration due to water deficiency
POTASSIUM
• the eighth or ninth most common element by
mass (0.2%) in the human body
Function
• important in neuron(brain and nerve)
function, and in influencing osmotic
balance between cells and the interstitial fluid
- Na+/K+-ATPase pump
• major cation of cell fluid
• maintaining fluid and electrolyte balance
– affects homeostasis, such as a steady heartbeat
• found in both plant and animal cells
– less found in processed foods
• deficiency
– hypertension
– most common electrolyte imbalance
– muscle weakness
• toxicity
– rare from food
– over consumption of supplements
CALCIUM
• atomic number : 20.
• atomic mass : 40.078 amu.
• soft gray alkaline earth metal,
• fifth most abundant element by mass in
the Earth's crust.
• fifth most abundant dissolved ion
in seawater by both molarity and mass,
after sodium, chloride, magnesium, and sulfate
• fifth most abundant element by mass in the
human body.
• absorption is affected by Vitamin D
Function
• cellular ionic messenger
• structural element in bone
– combined with phosphate to form hydroxylapatite,
is the mineral portion of human and animal bones
and teeth.
• muscle contraction
• exocytosis
• neurotransmitter release
• electrical conduction system of the heart
• blood clotting
• action potential
compounds
• Calcium carbonate (CaCO3) • Calcium
• Calcium hydroxide solution gluconate (Ca(C6H11O7)2)
(Ca(OH)2) • Calcium hypochlorite (Ca(OCl)2
• Calcium • Calcium
arsenate (Ca3(AsO4)2) permanganate (Ca(MnO4)2
• Calcium carbide (CaC2) • Calcium phosphate (Ca3(PO4)2)
• Calcium chloride (CaCl2) • Calcium phosphide (Ca3P2)
• Calcium cyclamate
• bone structure, calcium bank
• found primarily in milk and milk products
• deficiency
– limits mass & density
• growing years
• age related
– silent, no signals
PHOSPHORUS
• atomic number : 15
• multivalent nonmetal of the nitrogen group
• phosphorus as a mineral is almost always
present in its maximally oxidized state
• elemental phosphorus exists in two major
forms—white phosphorus and red
phosphorus
• due to its high reactivity, phosphorus is never
found as a free element on earth.
• 2nd most abundant
• energy metabolism, transport lipids, cell
membranes
• foods rich in protein, supply phosphorus
• PO43–
– component of DNA, RNA, ATP
• phospholipids
– that form all cell membranes.
• Calcium phosphate salts
– assist in stiffening bones
• Bones and teeth enamel
– Hydroxyapatite + calcium phosphate
– Water flouridation
Ca5(PO4)3OH + F- → Ca5(PO4)3F + OH-
MAGNESIUM
• atomic number : 12
• common oxidation number +2.
• alkaline earth metal
• seventh most abundant element in the Earth's
crust, where it constitutes about 2% by mass
• ninth in the known Universe as a whole
• 11th most abundant element by mass in
the human body
Function
• free element (metal) is not found naturally on
Earth - highly reactive
• occurs typically as the Mg2+ ion
• Mg-ATP – biological active form
• stability of all polyphosphate compounds in
the cells,
– including those associated with DNA and RNA
synthesis.
• over 300 enzymes
• minute amount, but critical
– energy metabolism, catalyst, ATP production
• critical to heart function
• toxicity is rare, but can be fatal
SULFUR
• atomic number : 16
• abundant, multivalent non-metal.
• at normal conditions, sulfur atoms form cyclic
octatomic molecules with chemical formula S8
• sulfur can react as either an oxidant or reducing
agent.
• Nature : can be found as the pure element
and as sulfide and sulfate minerals
• seventh or eighth most abundant element in
the human body by weight
– being about as common as potassium, and a little
more common than sodium or chlorine
• sulfur is not used by the body
– found in thiamin and several amino acids
• high sulfur content in
– skin, hair, nails
Function
• cysteine and methionine contain most of the
sulfur.
• present in all polypeptides, proteins,
and enzymes that contain these amino acids.
• Disulfide bonds (S-S bonds) formed between
cysteine residues in peptide chains are very
important in protein assembly and structure.
– These covalent bonds between peptide chains
confer extra toughness and rigidity
• cellular enzymes use prosthetic groups ending
with -SH moieties to handle reactions involving
acyl-containing biochemicals
• proteins, vitamins and hormones
– biotin and thiamine contain sulfur
• carrier of reducing hydrogen and its electrons,
for cellular repair of oxidation
– Glutathione and thioredoxin
• Inorganic sulfur forms a part of iron-sulfur
clusters as well as many copper, nickel, and
iron proteins.
– ferrodoxins, which serve as electron shuttles in
cells.
Organosulfur Compounds
Allicin R-cysteine

Methionine Diphenyl disulfide


Perfluorooctanesulfonic Dibenzothiopene
acid

Penicillin
The Trace Minerals
The Trace Minerals
• Needed in much smaller amounts
• 9 essential trace minerals
• Difficult to study due to the trace amounts needed by
the body
• Deficiency is rare
• Difficulty in assessing mineral status in human
• Interaction of trace minerals
• Food content dependent on soil content
• Animal sources of mineral are generally better
absorbed.
IRON
• atomic number : 26
• It is a metal in the first transition series.
• It is the most common element in the whole
planet Earth,
• It is the fourth most common element in the
Earth's crust
• Exists in a wide range of oxidation states, −2 to
+ 6,
– although +2 and +3 are the most common.
• forming complexes with molecular oxygen
in hemoglobin and myoglobin
– oxygen transport proteins in vertebrates.
• metal used at the active site of many
important redox enzymes
• Iron uptake is tightly regulated by the human
body
• No regulated physiological means of excreting
iron.
– Only small amounts of iron are lost daily due to
mucosal and skin epithelial cell sloughing
• Found in minute amount in every cell
• 15% is absorbed
• Heme iron Vs. Nonheme iron
– Heme found in animal products are
better absorbed than nonheme
• Ferrous iron (+2) Vs. Ferric iron (+3)
– +2 is better absorbed
• Vitamin C enhance absorption
– Forms chelate with +2
Functions of Iron
• Hemoglobin in red blood cells
– Transport oxygen and carbon dioxide
– High turnover, high demand for iron
• Myoglobin in muscle cells
• Electron transport chain cytochromes
• Enzyme cofactor within the Kreb’s cycle
• Immune function helps in breaking down
hydrogen peroxide
• Drug-detoxification pathway
ZINC
• atomic number : 30
• It is the first element in group 12 of the
periodic table.
• Chemically similar to magnesium, because
its ion is of similar size and its only common
oxidation state is +2.
• Zinc is the 24th most abundant element in the
Earth's crust and has five stable isotopes
• Contained at reactive center of enzymes
– alcohol dehydrogenase
– Carbonic anhydrase
• Zinc fingers are small protein structural
motifs that can coordinate one or
more zinc ions to help stabilize their folds.
– interaction modules that bind DNA,RNA, proteins,
or small molecules
• Hundred of specific enzymes
• serves as structural ions in transcription
factors and is stored and transferred
in metallothioneins
• second most abundant transition metal in
organisms after iron
• it is the only metal which appears in
all enzyme classes
Functions

• Cofactor to many enzymes


• Synthesis of nucleic acid
• Protein metabolism, cell membrane
• Wound healing, immune function, growth
• Development of sexual organs and bones
• Insulin function
• Component of superoxide dismutase
• In proteins, Zn ions are often coordinated to
the amino acid side chains of aspartic acid,
glutamic acid, cysteine and histidine
• Most zinc is in the brain, muscle, bones,
kidney, and liver, with the highest
concentrations in the prostate and parts of the
eye.
• has roles in the metabolism of RNA and
DNA, signal transduction, and gene expression.
It also regulates apoptosis
• stored in specific synaptic
vesicles by glutamatergic neurons and can
"modulate brain excitability“
• useful catalytic agent in hydroxylation and other
enzymatic reactions
• Communication b/w cells
– Salivary gland, prostate gland, immune system,
intestine
• Carbonic anhydrase
– converts CO2 into bicarbonate and the same
enzyme transforms the bicarbonate back
into CO2 for exhalation through the lungs
• Carboxypeptidase
– cleaves peptide linkages during digestion of
proteins
• Essential nutrient
• Better absorption from animal source
• Metallothionine : reservoir in the intestine
• blood plasma, zinc is bound to and
transported by albumin and transferrin \
COPPER
• atomic number : 29
• ductile metal with very
high thermal and electrical conductivity
• Copper(II) ions are water-soluble, where they
function at low concentration as bacteriostatic
substances, fungicides, and wood preservatives
• one s-orbital electron on top of a filled d-electron
shell and are characterized by high ductility and
electrical conductivity
• forms a rich variety of compounds
with oxidation states +1 and +2, which are
often called cuprous and cupric, respectively
• animals tissues : liver, muscle and bone.
Copper
• Absorption dependent on body’s needs
• Absorbed in stomach and duodenum
• Excess excreted via biliary route
• Absorption decreased with high vitamin C,
phytic acid, fiber, zinc, iron, certain amino
acids
Functions of Copper
• Increases iron absorption
• Formation of connective tissue
• Electron transport chain
• Formation of neurotransmitters
• Formation and maintenance of myelin
• Activate enzymes
• Immune system, blood clot, brain development,
cholesterol metabolism
• Copper is also a component of other proteins
associated with the processing of oxygen.
– cytochrome c oxidase : copper and iron cooperate
in the reduction of oxygen.
– superoxide dismutases: detoxify superoxides, by
converting it (by disproportionation) to oxygen
and hydrogen peroxide:
2 HO2 → H2O2 + O2
SELENIUM
• atomic mass : 78.96
• a nonmetal, whose properties are
intermediate between those of
sulfur and tellurium.
• rarely occurs in its elemental state in nature
• It is a component of the enzymes glutathione
peroxidase and thioredoxin reductase
• found in three deiodinase enzymes
• selenium is found in the amino
acids selenomethionine, selenocysteine,
and methylselenocysteine.
• Known to prevent Keshan disease
• Readily absorbed
• Excretion through the urine and feces
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Selenium as Antioxidant
IODINE
• atomic number : 53.
• iodine occurs mainly as a diatomic molecule I2,
not the atom.
• In nature, iodine is a relatively rare element,
ranking 47th in abundance.
• It is the heaviest essential element utilized
widely by life in biological functions
Iodide
• Absorbed along the GI tract
• Transported free or bound to proteins in the blood
• Thyroid hormone synthesis
• Regulates metabolic rate, growth, development
• Thyroid gland enlarges (goiter) with low intake of
iodide
• Goitrogens containing foods (raw turnips, rutabagas,
cauliflower, broccoli) inhibit function of the thyroid
gland
• Cretinism is a stunting of fetal growth and mental
development
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Thyroid Hormone Actions (Fig. 12-11)


MANGANESE
• atomic number : 25
• found as a free element in nature (often in
combination with iron), and in many minerals
• as a free element, manganese is a metal with
important industrial metal alloy uses,
• Manganese(II) ions function as cofactors for a
number of enzymes
– where they are essential in detoxification
ofsuperoxide free radicals..
• classes of enzymes
– oxidoreductases
– transferases
– hydrolases
– lyases
– isomerases
– ligases,
– Lectins
– integrins
Arginase
• Superoxide dismutase
– Mn-SOD
• In the human brain the manganese is bound
to manganese metalloproteins
– notably glutamine synthetase in astrocytes
MOLYBDENUM
• atomic number : 42
• does not occur as the free metal on Earth, but
rather in various oxidation states in minerals
• has several oxidation states, the most stable
being +4 and +6
Molybdenum cofactor
• forms compounds with various organic
molecules, including carbohydrates and amino
acids, it is transported throughout the human
body as MoO42−
• at least 50 molybdenum-containing enzymes
were known by 2002
• Xanthine oxidase
– Converts xanthine to uric acid
• use molybdenum bound at the active site in a
tricyclic molybdenum cofactor
• High levels of molybdenum can interfere with
the body's uptake of copper, producing copper
deficiency.
– prevents plasma proteins from binding to copper
– increases the amount of copper that is excreted
in urine
Other Minerals
• Boron
– Metabolism of steroid hormones
– Found in fruits, leafy vegetables., nuts
– Upper Level is 20 mg/day
• Nickel
– Activates enzymes
– Found in nuts, beans, grains, chocolate
– Upper Level is 1 mg/day
Silicon
• Involved in bone formation in small animals
• Found in plant foods, unrefined grains,
cereals, root vegetables
• No AI
• No Upper Level set
• Deficiency could effect brain and bone
formation
Ultraminerals
• Vanadium
– Enhances enzyme activities, mimics insulin
– Found in shell fish, mushrooms, grain
– No AI, Upper Level set at 1.8 mg/day
• Arsenic
– Poisonous
– Need in trace amounts
– Gene expression of stress proteins
– Found in fish, grains
– No AI, Upper Level set
Contaminant Minerals
• heavy metals
– lead
– mercury
– cadmium
• enter food through water, soil,
air pollution
• interfere with nutrients
• bioaccumulation
Major Mediators of Calcium and Phosphate
Balance

• Parathyroid hormone (PTH)

• Calcitriol (active form of vitamin D3)


Role of PTH
• Stimulates renal reabsorption of calcium
• Inhibits renal reabsorption of phosphate
• Stimulates bone resorption
• Inhibits bone formation and mineralization
• Stimulates synthesis of calcitriol

Net effect of PTH  ↑ serum calcium


↓ serum phosphate
Regulation of PTH

Low serum [Ca+2]  Increased PTH secretion

High serum [Ca+2]  Decreased PTH secretion


Role of Calcitriol
• Stimulates GI absorption of both calcium and
phosphate
• Stimulates renal reabsorption of both calcium
and phosphate
• Stimulates bone resorption

Net effect of calcitriol  ↑ serum calcium


↑ serum phosphate
Regulation of Calcitriol
Overview of Calcium-Phosphate Regulation
Different Forms of Calcium
At any one time, most of the calcium in the body exists as the
mineral hydroxyapatite, Ca10(PO4)6(OH)2.

Calcium in the plasma:


45% in ionized form (the physiologically active form)
45% bound to proteins (predominantly albumin)
10% complexed with anions (citrate, sulfate, phosphate)

To estimate the physiologic levels of ionized calcium in states of


hypoalbuminemia:

[Ca+2]Corrected = [Ca+2]Measured + [ 0.8 (4 – Albumin) ]


Overview of Biochemical Homeostasis
Overview of Calcium Balance
Overview of Phosphate Balance
FLOURINE
• atomic number : 9
• normal conditions, elemental fluorine is a pale
yellow gas of diatomic molecules,F2.
• Earth's crust, fluorine is more common: the
13th most abundant element.
• fluorine has a single stable isotope, fluorine-
19.
• Fluorine has the highest electron affinity of
any element, one of the strongest oxidizing
agents known.
• Fluorine forms stable compounds, fluorides
Fluoride
• Role in prevention of cavities

• Aids in synthesis of fluorapatite crystals


• Fluoride inhibits bacterial growth that may
cause cavities
• Fluoride prevents the acid produced by the
bacteria in plaque from dissolving, or de-
mineralizing, tooth enamel, the hard and
shiny substance that protects the teeth.
• Fluoride also allows teeth damaged by acid to
repair, or re-mineralize, themselves.
CHROMIUM
• atomic number : 24
• Chromium exhibits a wide range of
possible oxidation states, where the +3 state is
most stable energetically;
– +3 and +6 states are most commonly observed in
chromium compounds
– +1, +4 and +5 states are rare.
• trivalent chromium (Cr(III)) is required in trace
amounts for sugar and lipid metabolism
Function
• Role in Type II diabetes
• May increase the transport of glucose across the cell
membrane
• Enhances insulin action by boosting insulin receptor
activity
• Enhances the conversion of glucose to fat

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