INTRODUCTION TO BIOINORGANIC

CHEMISTRY

“The importance of the field stems from

the fact that life originated and
developed on the earth's crust, within an
inorganic environment”

Esperanza Galarza
2020
 LIVING THINGS
ORGANICS OR INORGANICS?
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 PERIODIC TABLE: BIOELEMENTS FOUND IN THE HUMAN BODY

Red: more abundant elements [g].

Blue: less abundant elements [trace – mg].
Green: very few elements [ultratrace or trace elements – μg].
essentiality under study. 4
 ESSENTIALITY: Deficiency in the nutritional sources leads to diseases, metabolic
abnormalities and causes severe and irreversible damage.
In an organism the essential elements are indispensable for growth,
reproduction and health.

MORE ABUNDANT: more than

98% of the weight of an adult
human.
ABUNDANTS ~ g
TRACE ~ mg
ULTRATRACE ~ μg

NON-ESSENTIAL: From geochemical origins or indicators of environmental exposure,

but they can enter the biochemistry of the body as therapeutic agents beneficial to
health due to their pharmacological action or they can become toxic. 5
✓ Heavy elements and some alloys are not present in biological systems
because they are not stable in water.

✓ Elements such as S, Cl, Se, Br and I can be found as anions and Na,
K, Mg, Ca and various transition metals such as cations. Groups 1, 2
and 3 associated with the ionic equilibrium model.

✓ Transition metals are also generally associated with aqueous ionic

chemistry and additionally with redox reactions.
✓ Organometallic: not very common in biology.

Through the series, they exhibit increased covalent chemistry, increased

Lewis acid strength not necessarily in equilibrium with their environment.
They become largely linked to biological organic molecules in which
equilibrium is more difficult to achieve.

✓ Group 12 ions such as Zn with strong Lewis acid properties while

maintaining little or no redox and ionic activity, are also usually bound
in biological systems.
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 HYDROGEN
1H: 1s1 (1e-) H+ H- H. Acquire Noble gas
configuration
Lewis Lewis strong COVALENT
strong acid base

➢Most abundant element in the universe and third most abundant

(after oxygen and silicon) on the earth's surface.
➢It was the first element to form after the big bang ~ 20’ years.
➢1671, Robert Boyle: Gas subsequently identified as Hydrogen.

Fe + H2SO4 or HCl Fe+2 (ac) + H2(g) Molecular form

➢ 1766, Henry Cavendish: Properties of hydrogen.

Lighter than air (colorless, odorless, highly volatile and explosive with gas mixtures with air).
Reaction with O2 to produce H2O.
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 THE EXISTENCE OF LIFE DEPENDS ON THE SPECIFIC PROPERTIES OF
HYDROGEN:
✓ The proximity of the electronegativities of
carbon and hydrogen.
Carbon 2.55; Hydrogen 2.20 → Low polarity bonds

✓ Hydrogen bonds when covalently bound with N

and O to form C-H and N-H.
✓ Proteins maintain their shape thanks to
hydrogen bonds.
✓ The only element that can be used to generate
energy from the electrolytic cell from light.
✓ As H+ (a cation) Lewis acid strong and
extremely mobile in protic medium such as
water and at the water/polymer biology DNA structure. The two nucleotide chains are
linked by hydrogen bonds (dashed lines).8
interfaces.
 SOME ASPECTS OF THE BIOLOGICAL CHEMISTRY OF HYDROGEN:
HYDROGEN IS A FUNDAMENTAL ELEMENT

• Hydrogen atoms may be involved in one or two electron

processes. Use in redox chemistry, in biological redox
reactions.

• The internal redox energy of organic molecules, C-H bonds

versus dioxygen, both derived from light, can be converted
into membrane systems, using oxidation / reduction, to
different ways of obtaining more usable energy.

• Hydrogen is transferred first as H-, then effectively as H.

and finally as H+, to produce proton gradients across the Produce ATP from
membranes in water. The reactions require, separate gradient of protons
movement of electrons. The strong Lewis acid H+ moves
freely, quickly connects to a kinetically controlled covalent
bond (redox chemistry, ionic acid base chemistry).
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 GENERAL ASPECTS
How can an element be captured (cell uptake) and incorporated into an
organism?
Plants are the primary source of chemical elements to animal life, although they depend on
microorganisms to obtain and differentially distribute some elements for their functions.

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https://www.pharmacologicalsciences.us/anti-tumor/mechanism-of-action-of-cisplatin.html

MECHANISM OF ACTION FOR CISPLATIN

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INTERRELATION BETWEEN THE BEHAVIORS OF A
BIOLOGICAL SYSTEM

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WAYS OF UNION OF THE METAL ON THE SURFACE OF THE
PROTEIN AND INSIDE THE PROTEIN FOLDING.

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 * Metal-ligand complex
(inorganic chemistry)

BIOINORGANIC * Organic groups

(organic chemistry)

* Heme group
(biology)

*
* *

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 1) Increased stability of the biomolecule.

2) Promotion of an essential 3)Modification of the

conformational change in protein. biomolecule function.

Metal
Role

4) Metallic or complex ions

can act as cofactors

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 1) The protein imposes an often-unusual rigid
arrangement of the ligand around the metal

2)The protein provides a way to

protect or guide the entry of 3) The main role of the protein is to offer an
substrates to the metal site environment to the specific metal ion, with
the coordinated ligands and others nearby
Protein
Role

4)Specialized molecules are

required to store and transport
metal ions in biological systems
Transferrine
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 Biological functions in which metal ions
participate
• The participation of calcium phosphates in the formation of bone
structures in higher organisms.
• In other organisms, hard tissues are associated with the
presence of SiO2 or calcium carbonates.
Structural
• Binding of a metal to a protein can provide:

- An active site for a catalytic process.

- It can serve to control the conformation of the polypeptide chain.
- Make the environment of the active site adopt a certain
configuration.
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 Biological functions in which metal ions
participate

The transport of oxygen, as well as its fixation or accumulation,

is normally carried out using proteins that contain iron
(hemoglobin, myoglobin, hemeritrins) or copper (hemocyanins). Activation
Because of its interaction with the metal center, the O2 and
molecule undergoes important changes in its electronic transport of
structure and reactivity as a process that receives the name of
activation and that is fundamental to enable the use of oxygen
oxygen
in biological systems.

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Biological functions in which metal ions
participate
Some other small molecules are also activated by
Activation interaction with metal centers, e.g., the N2 molecule
and that is activated in nitrogen-fixing systems, who is
transport transformed into ammonia. Molybdenum, iron or
of oxygen vanadium may be involved in this activation.

Also the CO2 molecule can be

biologically activated before its
transformation into methane,
processes in which iron and nickel
participate.
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 Biological functions in which metal ions
participate
• In certain biological systems, some of the metal atoms involved
can occur in different oxidation states (Fe(II)/Fe(III), Cu(I)/Cu
(II), Mo (IV)/Mo(V)/Mo(VI)), are used to transport electrons.

• In other words, they are systems that accept electrons from an

agent that is somewhat more reducing and transfer them to
Electron
another that is somewhat more oxidizing. Transport
• Some of these systems have even detected unusual oxidation
states (e.g. Fe(IV), Co(I), Ni(III)), which apparently can be
specifically stabilized by certain bioligands.
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Biological functions in which metal ions
participate

Catalytic In these systems the metal constitutes the active

site on which an oxide reduction reaction takes
functions in
place. Examples of metals commonly involved in
REDOX these types of functions are copper, iron, and
processes molybdenum.

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 Biological functions in which metal ions
participate
• Systems as hydrolases and phosphatases.
• The metals most commonly present in this type of system are
Catalytic
zinc and magnesium and, to a lesser extent, manganese and functions in
some other similar divalent cations. Also synthetases and
isomerases are part of this group.
acid-base
Other systems that also contain metals but cannot be classified within these
reactions
groups:
a) Systems that participate in the capture, transport and accumulation of metals.
b) Systems that participate in photochemical processes.
c) Systems that participate in detoxification mechanisms
d) Cationic systems that exercise control, regulation and transmission functions. In these,
the alkali and alkaline-earth cations participate.
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 METALLOBIOMOLECULES

PROTEIN NO PROTEIN

Transport and
Enzymes -Structural Funtion
accumulation proteins -Metals Uptake
-Oxide- -Regulatíon and Control
-Electron Transfer Systems
reductases
-Transport and -Photochemical Systems
-Transferases
accumulation of metals
-Hydrolases
-Transport and
-Lyases
Activation of O2
-Isomerases
(DETOXIFICATION)
-Ligases
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 GROUP 1: ALKALINE METALS
Biological aspects:
Sodium (Na+) and potassium (K+) ions:
High ionic mobility.
✓ They balance the negative charge of many body protein units. Lithium (Li)

[K+] intracellular = 150 mM; [K+] extracellular = 5 mM

[Na+] intracellular = 15 mM; [Na+] extracellular = 150 mM

✓ They maintain the osmotic pressure of the cells. Sodium (Na)

✓ They are responsible for the presence of electrical potential through the
Cell membrane -> Muscle contraction.

✓ Lithium deficiency causes behavioral disturbances (manic-depressive

disorders); An excess of lithium causes cardiac arrest. Optimum
concentration: 1 x 10-3 M Potassium (K)
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