‫‪Research For Applications of‬‬

‫‪Transition Elements‬‬

‫االسم ‪ :‬رنا هشام فهمى‬

‫الشعبة‪ :‬كيمياء انجليزي‬
‫الفرقة ‪ :‬الرابعة‬
‫مقدم الي د ‪ /‬هبة حيدر‬
Applications in biological field:

Traces of metals are essential for the biological

processes as about 30 - 40 % of all known proteins including
metalloenzymes require metal cofactors (e.g., Fe, Cu, Zn, Ni, Mn) for
their proper folding into an active three dimensional (3-D) structure.
Ligands having electron donor atoms like N, O, S, and P etc. may form
coordination bond with metal ion. Chelation causes drastic changes in
biological properties of ligands as well as metal moiety and in many
cases it causes synergistic effect of metal ion and ligand both.
A few well known metallopharmaceuticals include platinum (Pt)
anticancer agents cisplatin, carboplatin and oxaplatin, arsenic (As)
anticancer agent arsenic trioxide, orally active gold (Au) anti-
rheumatoid agent auranofin, selenium (Se) anti-inflammatory agent
ebselen, lithium (Li) anti-manic depressive agent lithium carbonate,
aluminum (Al) and zinc (Zn) anti-ulcer agents scralfate and polaprezinc.

DNA-metal Complex Interactions:

 DNA is the storage site of cellular information that is
accessed continuously for storing and dispensing
information required for existence. Thus, it acts as the
main intracellular target for those who thrive to develop
a new drug for innumerable diseases, especially cancer.
Added to the fact, small molecules that can bind and
react with specific DNA sites provide a means to access
and manipulate this cellular information creating the
desired results. There are many binding modes by which
the small molecules bind to the DNA which are covalent
and non-covalent binding. Cisplatin binds covalently
with the DNA thereby restricting its replication. Among
the non-covalent binding modes, intercalation, groove
binding and external electrostatic binding, intercalation is
the most important one because it invariably leads to
cellular degradation. Humungous reports are available
throughout the literature regarding the interactions of
V(IV), Ni(II), Co(II), Cu(II) and Zn(II) complexes with
DNA and still now many research groups have actively
involved in this field . Among the research groups, most
of them are concentrating only copper Schiff-base
complexes. For, copper is found in all living organisms
and is a vital trace element in redox chemistry, growth
and development. It is significant for the function of
several enzymes and proteins involved in energy
metabolism, respiration and DNA synthesis, particularly
cytochrome oxidase, superoxide dismutase (SOD),
ascorbate oxidase and tyrosinase. Copper is found to
bind DNA with high affinity than any other divalent
cation, thus promoting DNA oxidation.

Anti-microbial agents:

A review by Turel focuses on the crisis of decrease in

quinolone drug absorption when consumed
simultaneously with magnesium or aluminium antacids.
He reviewed selected crystal structures of quinolone-
metal compounds and their anti-microbial activities.

The reason for such behaviour is proposed to be the

chelate bonding of the quinolone to the metal. The
complex [Cu (cx)2]. 2H2O (where cx = cinoxacin) was
screened for activity against several bacteria [minimal
inhibitory concentration (MIC) values] showing the same
antimicrobial activity as the free ligand].
Using a series of Gram positive and Gram negative
bacterial strains, Scozzafava and his co-workers tested
zinc and copper ciprofloxacin complexes which showed
moderated antimicrobial effects. Very recently, Psomas
research group synthesized few quinolone cobalt(II)
complexes and tested their antimicrobial activity using
oxolinic acid (Hoxo) in the absence or presence of the
Lewis bases 2,2′-bipyridine (bipy), 2,2′-bipyridylamine
(bipyam), 1,10-phenanthroline (phen), pyridine (py) or 4-
benzylpyridine (4bzpy). Their antimicrobial activity
showed that the activity was similar to the free Hoxo.
The bacterial species K. pneumoniae (12 mm) and P.aeruginosa (11
mm). The Ni(II) mixed ligand complex
exhibited a higher zone of inhibition against E. coli (12
mm) and Zn(II) complex exhibited a higher zone of
inhibition against S. aureus (12 mm). From the above, it
was concluded that among the four mixed ligand metal
complexes, Cu(II) mixed ligand metal complex showed
higher antibacterial activity. In the case of antifungal
activity, Co(II) complex showed the higher zone of
inhibition against the fungal species C. albicans (13 mm)
and Ni(II) complex showed higher activity against A.
niger (8 mm). Overall, the antimicrobial activity of the
complexes is in the following order:
Cu (II)>Co(II)>Ni(II)>Zn(II).

The superior activity of the metal complexes may possibly be as a result

of increased lipophilic nature of the complexes attributed to chelation
and heteroatoms present in against the fungal species C.
albicans (13 mm) and Ni(II) complex showed higher
activity against A. niger (8 mm). Overall, the
antimicrobial activity of the complexes is in the
following order: Cu (II)>Co(II)>Ni(II)>Zn(II).

Anti-tumor agents:

Although there were multiple reports in recently

published papers about the ternary copper(II) complexes,
that are synthesized by the combination of a bidentate N-
donor heterocyclic ligand (phen, bpy or their substituted
derivatives) and other synthetic co-ligands (i.e., salicylic
acid], tetracycline derivatives, terpyridine], or
imidazolidine-2-thione]), with remarkable in vitro
cytotoxicity towards the human cancer cell lines, none
of these dealt with the directed synthesis of mixed ligand
copper(II) coordination compounds containing flavonoid
-inspired co-ligands.

Applications in chemical field:

 1. Transition metals are applied in the organic reactions.

Transition metals complex under goes a series of reactions that are

generally unlike those main group compounds. The most fundamental
is the simple coordination and dissociation of ligands.

Dissociation may also be achieved by destruction of a ligand. This is

often done by the oxidation of co and co2 using an amide oxide.

2. Transition metals are applied in the synthesis of metal hydride.

M=C=O + OH- == M-H + CO2

Here metal carbonyl group reacts with hydroxide to give metal hydride
and carbon dioxide.

Hydrides such as, sodium borohydride, lithium aluminium hydride,

diisobutylaluminium hydride (DIBAL) and super hydride, are commonly
used as reducing agents in chemical synthesis. The hydride adds to an
electrophilic center, typically unsaturated carbon.

Hydrides such as sodium hydride and potassium hydride are used as

strong bases in organic synthesis. The hydride reacts with the weak
Bronsted acid releasing H2.
Hydrides such as calcium hydride are used as desiccants, i.e. drying
agents, to remove trace water from organic solvents. The hydride reacts
with water forming hydrogen and hydroxide salt. The dry solvent can
then be distilled or vac transferred from the “solvent pot”.

Hydrides are of important in storage battery technologies such as

Nickel-metal hydride battery.

Various metal hydrides have been examined for use as a means of

hydrogen storage for fuel cell-powered electric cars and other purposed
aspects of a hydrogen economy.

Hydride intermediates are key to understanding a variety of

homogeneous and heterogeneous catalytic cycles as well as enzymatic
activity. Hydroformylation catalysts and hydrogenase both involve
hydride intermediates. The energy carrier NADH reacts as a hydride
donor or hydride equivalent.

3. Transition metal used in the complexes in fluorescence cell

imaging.

Transition metal complexes have often been proposed as useful

fluorophores for cell imaging due to their attractive photo physical
attributes, but until very recently their actual applications have been
scarce and largely limited to ruthenium complexes in DNA and oxygen
sensing.

4. Transition metal used as Catalysts.

Some transition metals are good catalysts. For example: most

automobiles have an emissions-control device called a catalytic
converter. This device contains a screen of platinum or palladium along
with rhodium, a metal. The presence of the transition metals, along
with the heat of combustion generated by an automobile engine causes
an exhaust coming from an internal combustion engine to be broken
down from partially burned hydrocarbon compounds into less harmful
compounds such as water vapour and carbon dioxide.