Redox Reactions

Understand the role movement of electrons plays in energy exchanges in cells

Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions. Oxidation and reduction occur in tandem. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called oxidation reduction reactions, or redox reactions.

Learning Objectives

  • Relate the movement of electrons to oxidation-reduction (redox) reactions
  • Describe how cells store and transfer free energy using ATP


 Electrons and Energy

Let’s imagine that you are a cell. You’ve just been given a big, juicy glucose molecule, and you’d like to convert some of the energy in this glucose molecule into a more usable form, one that you can use to power your metabolic reactions. How can you go about this? What’s the best way for you to squeeze as much energy as possible out of that glucose molecule, and to capture this energy in a handy form?

Fortunately for us, our cells—and those of other living organisms—are excellent at harvesting energy from glucose and other organic molecules, such as fats and amino acids. Here, we’ll go through a quick overview of how cells break down fuels, then look at the electron transfer reactions (redox reactions) that are key to this process.

Overview of fuel breakdown pathways

The reactions that allow energy to be extracted from molecules such as glucose, fats, and amino acids are called catabolic reactions, meaning that they involve breaking a larger molecule into smaller pieces. For example, when glucose is broken down in the presence of oxygen, it’s converted into six carbon dioxide molecules and six water molecules. The overall reaction for this process can be written as:

C6H12O6+6O26CO2+6H2OΔG=686kcal/mol\text{C}_6\text{H}_{12}\text{O}_6+6\text{O}_2\to{6}\text{CO}_2+6\text{H}_2\text{O}\,\,\,\,\,\,\,\,\,\,\Delta{G}=-686\text{kcal/mol}

This reaction, as written, is simply a combustion reaction, similar to what takes place when you burn a piece of wood in a fireplace or gasoline in an engine. Does this mean that glucose is continually combusting inside of your cells? Thankfully, not quite! The combustion reaction describes the overall process that takes place, but inside of a cell, this process is broken down into many smaller steps. Energy contained in the bonds of glucose is released in small bursts, and some of it can be captured in the form of adenosine triphosphate (ATP), a small molecule that is used to power reactions in the cell. Much of the energy from glucose is still lost as heat, but enough is captured to keep the metabolism of the cell running.

As a glucose molecule is gradually broken down, some of the breakdowns steps release energy that is captured directly as ATP. In these steps, a phosphate group is transferred from a pathway intermediate straight to ADP, a process known as substrate-level phosphorylation. Many more steps, however, produce ATP in an indirect way. In these steps, electrons from glucose are transferred to small molecules known as electron carriers. The electron carriers take the electrons to a group of proteins in the inner membrane of the mitochondrion, called the electron transport chain. As electrons move through the electron transport chain, they go from a higher to a lower energy level and are ultimately passed to oxygen (forming water). Energy released in the electron transport chain is captured as a proton gradient, which powers production of ATP by a membrane protein called ATP synthase. This process is known as oxidative phosphorylation. A simplified diagram of oxidative and substrate-level phosphorylation is shown below.

Simplified diagram showing oxidative phosphorylation and substrate-level phosphorylation during glucose breakdown reactions. Inside the matrix of the mitochondrion, substrate-level phosphorylation takes place when a phosphate group from an intermediate of the glucose breakdown reactions is transferred to ADP, forming ATP. At the same time, electrons are transported from intermediates of the glucose breakdown reactions to the electron transport chain by electron carriers. The electrons move through the electron transport chain, pumping protons into the intermembrane space. When these protons flow back down their concentration gradient, they pass through ATP synthase, which uses the electron flow to synthesize ATP from ADP and inorganic phosphate (Pi). This process of electron transport, proton pumping, and capture of energy from the proton gradient to make ATP is called oxidative phosphorylation. Figure 1. Image modified from "Etc4" by Fvasconcellos (public domain).


When organic fuels like glucose are broken down using an electron transport chain that ends with oxygen, the breakdown process is known as aerobic respiration (aerobic = oxygen-requiring). Most eukaryotic cells, as well as many bacteria and other prokaryotes, can carry out aerobic respiration. Some prokaryotes have pathways similar to aerobic respiration, but with a different inorganic molecule, such as sulfur, substituted for oxygen. These pathways are not oxygen-dependent, so the breakdown process is called anaerobic respiration (anaerobic = non-oxygen-requiring). Officially, both processes are examples of cellular respiration, the breakdown of down organic fuels using an electron transport chain. However, cellular respiration is commonly used as a synonym for aerobic respiration, and we’ll use it that way here[3].

Redox Reactions

Cellular respiration involves many reactions in which electrons are passed from one molecule to another. Reactions involving electron transfers are known as oxidation-reduction reactions (or redox reactions), and they play a central role in the metabolism of a cell. In a redox reaction, one of the reacting molecules loses electrons and is said to be oxidized, while another reacting molecule gains electrons (the ones lost by the first molecule) and is said to be reduced. You can remember what oxidation and reduction mean with the handy mnemonic “LEO goes GER”: Lose Electrons, Oxidized; Gain Electrons,Reduced. The formation of magnesium chloride is one simple example of a redox reaction:

Mg+Cl2Mg2++2Cl\text{Mg}+\text{Cl}_2\to\text{Mg}^{2+}+2\text{Cl}^{-}

In this reaction, the magnesium atom loses two electrons, so it is oxidized. These two electrons are accepted by chlorine, which is reduced. The atom or molecule that donates electrons (in this case, magnesium) is called the reducing agent, because its donation of electrons allows another molecule to become reduced. The atom or molecule that accepts the electrons (in this case, chlorine) is known as the oxidizing agent, because its acceptance of electrons allows the other molecule to become oxidized.

Redox reactions with carbon-containing molecules

When a reaction involves the formation of ions, as in the example with magnesium and chlorine above, it’s relatively easy to see that electrons are being transferred. Not all redox reactions involve the complete transfer of electrons, though, and this is particularly true of reactions important in cellular metabolism. Instead, some redox reactions simply change the amount of electron density on a particular atom by altering how it shares electrons in covalent bonds. As an example, let’s consider the combustion of butane:

Chemical reaction for butane combustion with diagrams of the molecules involved. Figure 2. Butane:
2C4H10+13O28CO2+10H2O2\text{C}_4\text{H}_{10}+13\text{O}_2\to8\text{CO}_2+10\text{H}_2\text{O}
What’s the electron-sharing situation at the start of the reaction? In butane, the carbon atoms are all bonded to other carbons and hydrogens. In
CC\text{C}-\text{C}
bonds, electrons are shared equally, and in
CH\text{C}-\text{H}
bonds, the
C\text{C}
atom has a very slight negative charge (since it’s a bit more electronegative than hydrogen). Similarly, when oxygens are bonded to one another in
O2\text{O}_2
, start subscript, 2, end subscript, electrons are shared very equally. After the reaction, however, the electron-sharing picture looks quite different. Oxygen is much more electronegative than carbon, so the in the
C=O\text{C}=\text{O}
 bonds of carbon dioxide, oxygen will “hog” the bond electrons. In the
OH\text{O}-\text{H}
 bonds of water, oxygen will similarly pull electrons away from the hydrogen atoms. Thus, relative to its state before the reaction, carbon has lost electron density (because oxygen is now hogging its electrons), while oxygen has gained electron density (because it can now hog electrons shared with other elements). It’s thus reasonable to say that carbon was oxidized during this reaction, while oxygen was reduced. (Hydrogen arguably loses a little electron density too, though its electrons were being hogged to some degree in either case.) Biologists often refer to whole molecules, rather than individual atoms, as being reduced or oxidized; thus, we can say that butane—the source of the carbons—is oxidized, while molecular oxygen—the source of the oxygen atoms—is reduced.

It’s important to understand that oxidation and reduction reactions are fundamentally about the transfer of electrons. In the context of biology, however, you may find it helpful to use the gain or loss of H and O atoms as a proxy for the transfer of electrons. As a general rule of thumb, if a carbon-containing molecule gains H atoms or loses O atoms during a reaction, it’s likely been reduced (gained electrons). Conversely, if it loses H atoms or gains O atoms, it’s probably been oxidized (lost electrons). For example, let’s go back to the reaction for glucose breakdown,
C6H12O6+6O26CO2+6H2O\text{C}_6\text{H}_{12}\text{O}_6+6\text{O}_2\to{6}\text{CO}_2+6\text{H}_2\text{O}
. In glucose, carbon is associated with H atoms, while in carbon dioxide, no Hs are present. Thus, we would predict that glucose is oxidized in this reaction.

We can confirm this if we look at the actual electron shifts involved, as in the video below:



Energy in Redox Reactions

Image of glucose, which has lots of C-C and C-H bonds with Figure 3. Click on the image for a larger view. Image based on similar diagram by Ryan Gutierrez.


Like other chemical reactions, redox reactions involve a free energy change. Reactions that move the system from a higher to a lower energy state are spontaneous and release energy, while those that do the opposite require an input of energy. In redox reactions, energy is released when an electron loses potential energy as a result of the transfer. Electrons have more potential energy when they are associated with less electronegative atoms (such as C or H), and less potential energy when they are associated with a more electronegative atom (such as O). Thus, a redox reaction that moves electrons or electron density from a less to a more electronegative atom will be spontaneous and release energy. For instance, the combustion of butane (above) releases energy because there is a net shift of electron density away from carbon and hydrogen and onto oxygen. If you’ve heard it said that molecules like glucose have “high-energy” electrons, this is a reference to the relatively high potential energy of the electrons in their
CC\text{C}-\text{C}
and
CH\text{C}-\text{H}
bonds.

Quite a bit of energy can be released when electrons in
CC\text{C}-\text{C}
and
CH\text{C}-\text{H}
 bonds are shifted to oxygen. In a cell, however, it’s not a great idea to release all that energy at once in a combustion reaction. Instead, cells harvest energy from glucose in a controlled fashion, capturing as much of it as possible in the form of ATP. This is accomplished by oxidizing glucose in a gradual, rather than an explosive, sort of way. There are two important ways in which this oxidation is gradual:

  • Rather than pulling all the electrons off of glucose at the same time, cellular respiration strips them away in pairs. The redox reactions that remove electron pairs from glucose transfer them to small molecules called electron carriers.
  • The electron carriers deposit their electrons in the electron transport chain, a series of proteins and organic molecules in the inner mitochondrial membrane. Electrons are passed from one component to the next in a series of energy-releasing steps, allowing energy to be captured in the form of an electrochemical gradient.


We’ll look at both redox carriers and the electron transport chain in more detail below.

The removal of an electron from a molecule, oxidizing it, results in a decrease in potential energy in the oxidized compound. The electron (sometimes as part of a hydrogen atom), does not remain unbonded, however, in the cytoplasm of a cell. Rather, the electron is shifted to a second compound, reducing the second compound. The shift of an electron from one compound to another removes some potential energy from the first compound (the oxidized compound) and increases the potential energy of the second compound (the reduced compound). The transfer of electrons between molecules is important because most of the energy stored in atoms and used to fuel cell functions is in the form of high-energy electrons. The transfer of energy in the form of electrons allows the cell to transfer and use energy in an incremental fashion—in small packages rather than in a single, destructive burst. This module focuses on the extraction of energy from food; you will see that as you track the path of the transfers, you are tracking the path of electrons moving through metabolic pathways.

Electron Carriers

Electron carriers, sometimes called electron shuttles, are small organic molecules that readily cycle between oxidized and reduced forms and are used to transport electrons during metabolic reactions. There are two electron carriers that play particularly important roles during cellular respiration: NAD+ (nicotinamide adenine dinucleotide, shown below) and FAD (flavin adenine dinucleotide). Both NAD+ and FAD can serve as oxidizing agents, accepting a pair of electrons, along with one or more protons, to switch to their reduced forms. NAD+  accepts two electrons and one H+ to become NADH, while FAD accepts two electrons and two H+ to become FADH2. NAD+ is the primary electron carrier used during cellular respiration, with FAD participating in just one (or two sometimes two) reactions.

This illustration shows the molecular structure of NAD^{+} and NADH. Both compounds are composed of an adenine nucleotide and a nicotinamide nucleotide, which bond together to form a dinucleotide. The nicotinamide nucleotide is at the 5' end, and the adenine nucleotide is at the 3' end. Nicotinamide is a nitrogenous base, meaning it has nitrogen in a six-membered carbon ring. In NADH, one extra hydrogen is associated with this ring, which is not found in NAD^{+}. Figure 4. The oxidized form of the electron carrier (NAD+) is shown on the left and the reduced form (NADH) is shown on the right. The nitrogenous base in NADH has one more hydrogen ion and two more electrons than in NAD+.


As shown in the image above, NAD+ is a small organic molecule whose structure includes the RNA nucleotide adenine. (FAD is a similar type of molecule, although its functional groups are different.) Both molecules are B vitamin derivatives, with NAD+ produced from niacin and FAD produced from riboflavin. NAD+  and FAD are coenzymes, organic molecules that serve as helpers during enzyme-catalyzed reactions, and they receive electrons and protons as part of these reactions. Specifically, both NAD+  and FAD serve as cofactors for enzymes called dehydrogenases, which remove one or more hydrogen atoms from their substrates.

The Electron Transport Chain

In their reduced forms, NADH and FADH2 carry electrons to the electron transport chain in the inner mitochondrial membrane. They deposit their electrons at or near the beginning of the transport chain, and the electrons are then passed along from one protein or organic molecule to the next in a predictable series of steps. Importantly, the movement of electrons through the transport chain is energetically “downhill,” such that energy is released at each step. In redox terms, this means that each member of the electron transport chain is more electronegative (electron-hungry) that the one before it, and less electronegative than the one after[4]. NAD+, which deposits its electrons at the beginning of the chain as NADH, is the least electronegative, while oxygen, which receives the electrons at the end of the chain (along with H+) to form water, is the most electronegative. As electrons trickle “downhill” through the transport chain, they release energy, and some of this energy is captured in the form of an electrochemical gradient and used to make ATP.

ATP in Living Systems

A living cell cannot store significant amounts of free energy. Excess free energy would result in an increase of heat in the cell, which would result in excessive thermal motion that could damage and then destroy the cell. Rather, a cell must be able to handle that energy in a way that enables the cell to store energy safely and release it for use only as needed. Living cells accomplish this by using the compound adenosine triphosphate (ATP). ATP is often called the “energy currency” of the cell, and, like currency, this versatile compound can be used to fill any energy need of the cell. How? It functions similarly to a rechargeable battery.

When ATP is broken down, usually by the removal of its terminal phosphate group, energy is released. The energy is used to do work by the cell, usually by the released phosphate binding to another molecule, activating it. For example, in the mechanical work of muscle contraction, ATP supplies the energy to move the contractile muscle proteins. Recall the active transport work of the sodium-potassium pump in cell membranes. ATP alters the structure of the integral protein that functions as the pump, changing its affinity for sodium and potassium. In this way, the cell performs work, pumping ions against their electrochemical gradients.

ATP Structure and Function

This illustration shows the molecular structure of ATP. This molecule is an adenine nucleotide with a string of three phosphate groups attached to it. The phosphate groups are named alpha, beta, and gamma in order of increasing distance from the ribose sugar to which they are attached. Figure 5. ATP (adenosine triphosphate) has three phosphate groups that can be removed by hydrolysis to form ADP (adenosine diphosphate) or AMP (adenosine monophosphate).The negative charges on the phosphate group naturally repel each other, requiring energy to bond them together and releasing energy when these bonds are broken.


At the heart of ATP is a molecule of adenosine monophosphate (AMP), which is composed of an adenine molecule bonded to a ribose molecule and to a single phosphate group (Figure 5). Ribose is a five-carbon sugar found in RNA, and AMP is one of the nucleotides in RNA. The addition of a second phosphate group to this core molecule results in the formation of adenosine diphosphate (ADP); the addition of a third phosphate group forms adenosine triphosphate (ATP).

The addition of a phosphate group to a molecule requires energy. Phosphate groups are negatively charged and thus repel one another when they are arranged in series, as they are in ADP and ATP. This repulsion makes the ADP and ATP molecules inherently unstable. The release of one or two phosphate groups from ATP, a process called dephosphorylation, releases energy.

Energy from ATP

Hydrolysis is the process of breaking complex macromolecules apart. During hydrolysis, water is split, or lysed, and the resulting hydrogen atom (H+) and a hydroxyl group (OH) are added to the larger molecule. The hydrolysis of ATP produces ADP, together with an inorganic phosphate ion (Pi), and the release of free energy. To carry out life processes, ATP is continuously broken down into ADP, and like a rechargeable battery, ADP is continuously regenerated into ATP by the reattachment of a third phosphate group. Water, which was broken down into its hydrogen atom and hydroxyl group during ATP hydrolysis, is regenerated when a third phosphate is added to the ADP molecule, reforming ATP.

Obviously, energy must be infused into the system to regenerate ATP. Where does this energy come from? In nearly every living thing on earth, the energy comes from the metabolism of glucose. In this way, ATP is a direct link between the limited set of exergonic pathways of glucose catabolism and the multitude of endergonic pathways that power living cells.

Phosphorylation

Recall that, in some chemical reactions, enzymes may bind to several substrates that react with each other on the enzyme, forming an intermediate complex. An intermediate complex is a temporary structure, and it allows one of the substrates (such as ATP) and reactants to more readily react with each other; in reactions involving ATP, ATP is one of the substrates and ADP is a product. During an endergonic chemical reaction, ATP forms an intermediate complex with the substrate and enzyme in the reaction. This intermediate complex allows the ATP to transfer its third phosphate group, with its energy, to the substrate, a process called phosphorylation. Phosphorylation refers to the addition of the phosphate (~P). This is illustrated by the following generic reaction:

A + enzyme + ATP → [A − enzyme − ~P] → B + enzyme + ADP + phosphate ion

When the intermediate complex breaks apart, the energy is used to modify the substrate and convert it into a product of the reaction. The ADP molecule and a free phosphate ion are released into the medium and are available for recycling through cell metabolism.

Substrate Phosphorylation

ATP is generated through two mechanisms during the breakdown of glucose. A few ATP molecules are generated (that is, regenerated from ADP) as a direct result of the chemical reactions that occur in the catabolic pathways. A phosphate group is removed from an intermediate reactant in the pathway, and the free energy of the reaction is used to add the third phosphate to an available ADP molecule, producing ATP (Figure 6). This very direct method of phosphorylation is called substrate-level phosphorylation.

This illustration shows a substrate-level phosphorylation reaction in which the gamma phosphate of ATP is attached to a protein. Figure 6. In phosphorylation reactions, the gamma phosphate of ATP is attached to a protein.


Oxidative Phosphorylation

Most of the ATP generated during glucose catabolism, however, is derived from a much more complex process, chemiosmosis, which takes place in mitochondria (Figure 7) within a eukaryotic cell or the plasma membrane of a prokaryotic cell.

This illustration shows the structure of a mitochondrion, which has an outer membrane and an inner membrane. The inner membrane has many folds, called cristae. The space between the outer membrane and the inner membrane is called the intermembrane space, and the central space of the mitochondrion is called the matrix. ATP synthase enzymes and the electron transport chain are located in the inner membrane Figure 7. The mitochondria (Credit: modification of work by Mariana Ruiz Villareal)


Chemiosmosis, a process of ATP production in cellular metabolism, is used to generate 90 percent of the ATP made during glucose catabolism and is also the method used in the light reactions of photosynthesis to harness the energy of sunlight. The production of ATP using the process of chemiosmosis is called oxidative phosphorylation because of the involvement of oxygen in the process.

Mitochondrial Disease Physician

What happens when the critical reactions of cellular respiration do not proceed correctly? Mitochondrial diseases are genetic disorders of metabolism. Mitochondrial disorders can arise from mutations in nuclear or mitochondrial DNA, and they result in the production of less energy than is normal in body cells. In type 2 diabetes, for instance, the oxidation efficiency of NADH is reduced, impacting oxidative phosphorylation but not the other steps of respiration. Symptoms of mitochondrial diseases can include muscle weakness, lack of coordination, stroke-like episodes, and loss of vision and hearing. Most affected people are diagnosed in childhood, although there are some adult-onset diseases. Identifying and treating mitochondrial disorders is a specialized medical field. The educational preparation for this profession requires a college education, followed by medical school with a specialization in medical genetics. Medical geneticists can be board certified by the American Board of Medical Genetics and go on to become associated with professional organizations devoted to the study of mitochondrial diseases, such as the Mitochondrial Medicine Society and the Society for Inherited Metabolic Disease.

In Summary: ATP in Living Systems

ATP functions as the energy currency for cells. It allows the cell to store energy briefly and transport it within the cell to support endergonic chemical reactions. The structure of ATP is that of an RNA nucleotide with three phosphates attached. As ATP is used for energy, a phosphate group or two are detached, and either ADP or AMP is produced. Energy derived from glucose catabolism is used to convert ADP into ATP. When ATP is used in a reaction, the third phosphate is temporarily attached to a substrate in a process called phosphorylation. The two processes of ATP regeneration that are used in conjunction with glucose catabolism are substrate-level phosphorylation and oxidative phosphorylation through the process of chemiosmosis.

Check Your Understanding

Answer the question(s) below to see how well you understand the topics covered in the previous section. This short quiz does not count toward your grade in the class, and you can retake it an unlimited number of times.

Use this quiz to check your understanding and decide whether to (1) study the previous section further or (2) move on to the next section.


  1. Reece, "J. B., Urry, L. A., Cain, M. L., Wasserman, S. A., Minorsky, P. V., and Jackson, R. B. (2011). Cellular respiration and fermentation. In Campbell biology (10th ed., pp. 162-184). San Francisco, CA: Pearson."
  2. Ibi. ""
  3. Reece, "J. B., Urry, L. A., Cain, M. L., Wasserman, S. A., Minorsky, P. V., and Jackson, R. B. (2011). Cellular respiration and fermentation. In Campbell biology (10th ed., pp. 162–184). San Francisco, CA: Pearson."
  4. Ibi. ""

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