OXIDATION AND REDUCTION:

USING ELECTRONS TO TRANSFER ENERGY

The key to biological energy transformations is the transfer of

energy from one molecule to another. One of the two most

common mechanisms for transferring energy in biochemical

reactions involves the exchange of electrons between molecules.

These types of reactions are known as oxidation-reduction (or

redox) reactions. A loss of one or more electrons is known as

oxidation and the molecule that loses electrons is said to be

oxidized. In biochemical reactions, an oxidized molecule is

When you enter the shade of the forest, a significant cooling

effect is often felt. What properties of leaves do you think are

responsible for this effect? Would you expect the effect to be

stronger in a deciduous forest or a pine forest?

32 Photosynthesis and Respiration

often referred to as an electron donor. Conversely, the gain of

an electron is known as reduction and the molecule that gains the

electron, the electron acceptor, is said to be reduced. Note that

an oxidation-reduction reaction does not necessarily require

the participation of oxygen, only that electrons be exchanged.

The process is called oxidation solely because oxygen is one of

the most common electron acceptors. Another point to note

is that electrons can not exist in a free state, so the oxidation

of one molecule must be accompanied by the reduction of

another molecule.

A Short Course in Bioenergetics 33

Entropic Doom

The second law of thermodynamics can be formulated in a number of ways.

The most celebrated version of the second law is the one expressed by R. J.
Clausius, a 19th-century German physicist and mathematician: “The energy

of the universe is constant; the entropy of the universe tends toward a

maximum.” Commonly known as Clausius’ Dictum, the second law conveys

the notion that entropy is an index of exhaustion.

As the universe ages, it steadily loses its capacity for spontaneous change

(i.e., free energy decreases) and becomes progressively more disordered

(i.e., entropy increases). As a result, all of the energy in the universe may one

day be randomly and uniformly distributed. No stars would shine, planets

would no longer rotate on their axes, and the universe would reach a state of

total equilibrium, resulting in an entropic doom. However, this won’t happen

for a few years. The best guess tells us that the universe is 14 billion years

old. The Earth formed about 5 billion years ago and the first living cells

appeared about 4.5 billion years ago. The first vertebrates appeared less

than 500 million years ago and humans have been around for less than one

million years. It appears that our sun has at least another 5 billion years of

hydrogen fuel remaining and the universe should stave off entropic doom for

perhaps another 100 billion years.

Both photosynthesis and respiration are examples of oxidation-

reduction reactions. In photosynthesis, water is oxidized to

molecular oxygen and the electrons are used to reduce carbon

dioxide to sugar. Respiration is just the opposite—sugar or other

organic molecules are oxidized and the electrons are used to

reduce oxygen and form water.

An electron donor is also known as a reducing agent because,

by donating electrons, it causes another molecule to become

reduced. Conversely, an electron acceptor is known as an oxidizing

agent. As we will see in the next chapter, one consequence

of the light reactions of photosynthesis is to generate a strong

reducing agent that carries sufficient energy to reduce carbon

dioxide. Oxygen, on the other hand, is a strong oxidizing agent

that serves as the final acceptor for electrons stripped from

glucose during respiration.

In both photosynthesis and respiration, the electron transfers

are not simple, one-step reactions but involve mobile electron

carriers that shuttle electrons from one intermediate to another.

The two most common electron carriers are nicotinamide adenine

dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate

(NADP) (Figure 2.2). The role of these carriers in redox reactions

can be illustrated by one of the reactions in respiration. In this

reaction, malic acid (or malate) is oxidized to oxaloacetic acid

(or oxaloacetate). The half-reaction for malate oxidation is:

malate ———————> oxaloacetate + 2e- + 2H+

The electrons removed from malate are transferred to NAD+,

the oxidized form of NAD, thus reducing NAD+ to NADH. The

reduction of NAD+ is shown by the second half-reaction:

Look around. Can you see examples of oxidation in your everyday

environment? (Hint: we often call the products of oxidation rust

and corrosion.)

34 Photosynthesis and Respiration

NAD+ + 2e- + 2H+ ———————> NADH + H+

Combining these two half-reactions gives us the overall reaction

in which the reduction of NAD+ is coupled to the oxidation

of malate (Figure 2.3):

malate + NAD+ ——————> oxaloacetate + NADH + H+

NADH is a strong reducing agent that can be used to reduce

another molecule elsewhere in the cell.