REDOX REACTIONS in BIOLOGICAL SYSTEM

4. Oxidation and Reduction

In living organisms, both energy releasing and capturing processes consist mainly of redox reactions. Redox reactions occur when there is a transfer of electrons between an electron donor and electron acceptor. Oxidation refers to a reaction in which oxygen combined with an element or compound, e.g., the reaction of magnesium with oxygen to form magnesium oxide or the combination of carbon monoxide with oxygen to form carbon dioxide. In the process, the compound gives up electrons to the oxygen in forming a chemical bond. Thus, electrons released (lost) is oxidation with an increase in oxidation number.

Redox Pairs and energy

Reduction refers to a decrease in the amount of oxygen in a substance, and gain electrons, or a decrease in oxidation number, whether or not oxygen itself is actually involved in the reaction. The tendency for a specific conjugate redox pair to lose an electron is called redox potential. Electrons flow spontaneously from electronegative redox pairs to those that are more positive. As they flow, electrons lose energy. A significant portion of free energy generated as electrons move from NADH to oxygen in the electron transport system is used to synthesize ATP. In many metabolic processes, energy is required to move electrons from redox pairs with more positive reduction potentials to those with more negative reduction potentials.

Redox
For examples, in photosynthetic pathways, light energy is needed to drive electrons from electron donors (such as water), to electron acceptors with more negative reduction potentials. The energized electrons eventually flow back to acceptors with more positive reduction potentials, thus providing energy for ATP synthesis and carbon dioxide reduction to form carbohydrates.

Energy need of all organisms are provided directly or indirectly by solar energy

Conversion of mass into energy is a very large increase in disorder.

5.2 First Law of Thermodynamics The law of energy conservation

Energy cannot be created or destroyed. Energy is conserved in any closed system ( a system without any transfer of energy and matter in and out). E.g. The food pyramid: photosynthetic organisms at the base capture light energy as primary producers, herbivores and carnivores derive their energy ultimately from the primary producers.

However, first law alone cannot explaincube in a glass of water at room living processes. Why place an ice

temperature and the ice melts instead of freezing the whole glass of water? (directional control) Why cant we mix carbon dioxide and water to make paper? Why some reactions are reversible and some are irreversible? We thus need the second Law of thermodynamics, as biochemical processes always have tight control of their directions and rates of reactions by enzymes.

5.3 Second Law of Thermodynamics:

Any system tends to become increasingly disorganized. In any spontaneous process, there is always an increase in entropy (S). Entropy describes the number of the possible microscopic configurations of the system. The total entropy change in any reaction that occurs spontaneously must be greater than zero. Considering work, heat and energy together, entropy is a state function of a thermodynamic system defined by the differential quantity dS = dQ / T, where dQ is the amount of heat absorbed in a reversible process in which the system goes from the one state to another, and T is the absolute temperature.

5.4 Free Energy Concept

Considering the second law in open systems, as biological systems are always opened to exchange energy and matter with its environment.

Using concepts of entropy () and enthalpy (, heat content), the concept of Gibbs free energy to include both
energy and entropy: G = H - TS. Change of free energy: G =H - TS A thermodynamically favoured process tends in the direction that minimizes free energy, results in a negative G, (H TS) < 0, this is also one way of stating the second law.

The variation of reaction spontaneity (sign of G) with the signs of H andS.

H S G = H - TS
The reaction is both enthalipically favoured (exothermic) and entropically favoured. It is spontaneous (exergonic at all temperatures). The reaction is enthalpically favoured but not entropically, it is spontaneous only when temperatures below T= H/ S

+ +

The reaction is endothermic and enthalpically opposed but entropically favoured. It is spontaneous at temperature above T= H/ S

Both enthalpically and entropically opposed, endergonic at all temperatures

Chemical potential and chemical equilibrium:

GA = GA + RT In[A]

G= Gibbs free energy, GA is standard-state

value of the chemical potential for compound A, and GA also consider the concentration of A and temperature. For the reaction aA + bB = cC + dD
G = G products G reactants G = G + RT In [C]c [D]d/ [A]a [B]b G = 0, G = - RT In Keq

Standard free energy changes are additive

Glu + Pi = Glu 6P + H2O ATP + H2O = ADP + Pi Glu + ATP = ADP + Glu6P

dG = 13.8 kJ/mol dG = -30.5 kJ/mol dG = -16.7 kJ/mol

The standard Free Energy change of a reaction is an alternative mathematical way of expression of equilibrium constant. It is defined as the Free energy change of a reaction at standard conditions (at 298 K and 1 atm pressure when the initial concentrations of reactants and products are at 1M each. aA+bB = cC+dD equilibrium constant Keq = [C]c[D]d/[A]a[B]b

Actual free energy change depends on reactants and product concentration

The rate of a reaction

However, the G values dictate the direction NOT the rate of the reaction The rate of a reaction is determined by kinetic parameters and is restricted by activation energy. Many biochemical reactions with a negative G value, however could not have happened without lowering their activation energy. Appropriate enzyme is needed to make the reaction become kinetically feasible and proceed at a much faster rate.

5.5 Steady-state thermodynamics

1. The above laws state that the reversible reactions tend to operate to approach equilibrium, but living processes seem to contradict this ever increasing entropy scenario. 2. Living things are however never at equilibrium, the cells maintains itself at a stage far from equilibrium with its surrounding. Otherwise, no useful work can be done when at equilibrium, entropy is at maximum, and G = 0. 3. At steady state, output of energy and matters is continuously replaced by the input of an exactly the same amount of matters and energy. A steady state is also very responsive to its surrounding environment (or system). We need energy to sustain all living processes. 4. Solar energy is captured in plants as sugars (glucose) to be converted into high energy compounds like ATP for living processes. For human, we need to eat to obtain energy for biological processes and our normal activities.

Phosphoryl group transfer and ATP as currency of free energy

ATP is generated during catabolic reaction and the free energy of ATP hydrolysis is used in synthetic reactions, to do mechanical work or to produce light (in fire fly), sound or to conduct neuronal action potential. Basis of high energy of hydrolysis of ATP: 1. Resonance stabilization of products 2. Electrostatic repulsion between negatively charged oxygen atoms in ATP 3. High solvation energy of products ATP is more stable than other phosphoanhydride compound

Electrons are transferred from one molecule (electron donor) to another (electron acceptor) in one of the four different ways; 1. Direct electron transfers: Fe2+ + Cu2+ = Fe3+ + Cu+ 2. As hydrogen atom: AH2 = A + 2e- + 2H+ B + 2e- + 2H+ = BH2 -------------------------------AH2 + B = A + BH2 3. As hydride ion (:H-): As in case of NAD-linked dehydrogenases Transfer of two electron. 4. Through direct combination with oxygen: Covalent incorporation of oxygen into an organic molecule. In biological systems oxidation is often referred as dehydrogenation.

Standard reduction potential: (Eo)

It is the electric potential generated by a redox reaction against hydrogen electrode, when the concentration of reduced and oxidized species are at 1 M concentration. Reduction potential of a half-cell depends on the the activity of reduced and oxidized species which is approximated by their concentrations. Nernst Equation: E = Eo + RT/nf ln [electron acceptor]/[electron donor] N= number of electrons transferred, f= Faradays constant. At 25 oC, the equation is; E = Eo + 0.026V/n ln [electron acceptor]/[electron donor] Standard reduction potential is used for free energy change calculation as follows: DG = -nf DE or DGo = -nf DEo