BLOK BIOMEDIK II

Tahun ajar 2016/2017

BIOLOGIC OXIDATION

Ika Yustisia
Departement of Biochemistry
FACULTY OF MEDICINE HASANUDDIN UNIVERSITY
Corresponding email: ikayustisia@gmail.com
 Outline and objectives
• Definition
• Understanding the reduction potential (E’0)
• Four groups of oxidoreductases
– Oxidases
– Dehydrogenases
– Hydroperoxidases
– Oxygenases
 Definition
Oxidation–reduction
Oxidation–reduction reactions always involve a
pair of chemicals:
 An electron donor → oxidized in the reactions →
reductant = reducing agent
 An electron acceptor → reduced in the reaction →
oxidant = oxidizing agent
LEO GER
Loss of Electrons Oxidation
Gain of Electrons Reduction
 Definition
Oxidation–reduction
Compounds are oxidized in the body in
essentially three ways:
(1) The transfer of electrons from the compound
as a hydrogen atom or a hydride ion
(2) The direct addition of oxygen from O2
(3) The direct donation of electrons (e.g., Fe2+ →
Fe3+)
 Definition
Oxidation–reduction
 Definition
Oxidation–reduction
Understanding the reduction potential (E’0)

• Consider a substance that can exist in

– A reduced form X-
– An oxidized form X
• The pair is called a redox couple X-:X
• The reduction potential of this couple can be
determined by measuring the electromotive
force generated by an apparatus called a
sample half-cell connected to a standard
reference half-cell
 Understanding the reduction potential (E’0)
• The sample half-cell consists of
an electrode immersed in a
solution of 1 M reductant (X-)
and 1 M oxidant (X)
• The standard reference half-
cell consists of an electrode
immersed in a 1 M H+ solution
that is in equilibrium with H2
gas at 1 atmosphere (1 atm) of
pressure.
 Understanding the reduction potential (E’0)
• If the reaction proceeds in the direction:

• The reactions in the half-cells (referred to as half-

reactions or couples ) must be
• The reduction potential of the couple is X-:X the
observed voltage at the start of the experiment
• The donor of electrons, in this case X- → reductant

• The acceptor of electrons, H+ → oxidant

Understanding the reduction potential (E’0)
Understanding the reduction potential (E’0)
 Understanding the reduction potential (E’0)
• A negative reduction potential means
that the oxidized form of a substance
has lower affinity for electrons than does H2
• A positive reduction potential means
that the oxidized form of a substance has
higher affinity for electrons

• A strong reducing agent (such as NADH) is poised to

donate electrons and has a negative reduction potential
• A strong oxidizing agent (such as O2) is ready to accept
electrons and has a positive reduction potential.
 Understanding the reduction potential (E’0)
• The standard free-energy change ΔG0’is related to the
change in reduction potential ΔE’0

• n: number of electrons transferred

• F: Faraday constant 96,48 kJ mol-1V-1 = 23,06 kcal mol-1V-1
• ΔE’0 is in volts
• ΔG0 is in kilojoules or kilocalories per mole
 Understanding the reduction potential (E’0)
• The reduction of pyruvate by NADH, catalyzed by
lactate dehydrogenase
 Understanding the reduction potential (E’0)
• The reduction of pyruvate by NADH, catalyzed by
lactate dehydrogenase
 Understanding the reduction potential (E’0)
• The reduction of pyruvate by NADH, catalyzed by
lactate dehydrogenase
 Understanding the reduction potential (E’0)
• Hitunglah standar energi bebas ΔG0’ untuk reaksi
berikut:
 Four groups of oxidoreductases
• Oxidases

• Oxidases catalyze the removal of hydrogen from a

substrate using oxygen as a hydrogen acceptor
• They form water or hydrogen peroxide as a reaction
product
• Cytochrome oxidase - the terminal protein complex in the
electron transport chain
• Flavoprotein enzymes contain flavin mononucleotide (FMN) or
flavin adenine dinucleotide (FAD) as prosthetic groups. FMN
and FAD are formed in the body from the vitamin riboflavin.
Examples: xanthine oxidase, aldehyde dehydrogenase
 Four groups of oxidoreductases
• Oxygenases incorporate one or both of the atoms of oxygen into
the organic substrate
• Monooxygenases: enzymes that incorporate one atom of oxygen
into the substrate and the other into H2O, are often named
hydroxylases

• Dioxygenases, enzymes that incorporate both atoms of oxygen

into the substrate, are used in the pathways for converting
arachidonate into prostaglandins, thromboxanes, and
leukotrienes.
 Four groups of oxidoreductases
• Dehydrogenases cannot use oxygen as a hydrogen acceptor
• Transfer of hydrogen from one substrate to another in a coupled
oxidation–reduction reaction

• Transfer of electrons in the respiratory chain of electron transport

from substrate to oxygen
 Four groups of oxidoreductases
• Dehydrogenases
• Many dehydrogenases depend on nicotinamide coenzymes
these dehydrogenases use nicotinamide adenine
dinucleotide (NAD+) or nicotinamide adenine dinucleotide
phosphate (NADP+)—or both—which are formed in the body
from the vitamin niacin

• The flavin groups such as FMN and FAD are also associated
with dehydrogenases
 Four groups of oxidoreductases
• Hydroperoxidases use hydrogen peroxide or an organic
peroxide as substrate
• Two type of enzymes found both in animals and plants
fall into the hydroperoxidase category:
• Peroxidases
• Catalase