Laws of Thermodynamics

Life can exist only where molecules and cells remain organized. All cells need energy to maintain organization. Physicists define energy as the ability to do work; in this case, the work is the continuation of life itself.

The behavior of energy has been expressed in terms of reliable observations known as the laws of thermodynamics. There are two such laws. The first law of thermodynamics states that energy can neither be created nor destroyed. This law implies that the total amount of energy in a closed system (for example, the universe) remains constant. Energy neither enters nor leaves a closed system.

Within a closed system, energy can change, however. For instance, the chemical energy in gasoline is released when the fuel combines with oxygen and a spark ignites the mixture within a car's engine. The gasoline's chemical energy is changed into heat energy, sound energy, and the energy of motion.

The second law of thermodynamics states that the amount of available energy in a closed system is decreasing constantly. Energy becomes unavailable for use by living things because of entropy, which is the degree of disorder or randomness of a system. The entropy of any closed system is constantly increasing. In essence, any closed system tends toward disorganization.

Unfortunately, the transfers of energy in living systems are never completely efficient. Every body movement, every thought, and every chemical reaction in the cells involves a shift of energy and a measurable loss of energy in the process. For this reason, considerably more energy must be taken into the system than is necessary to carry out the actions of life.


Chemical Reactions

Most chemical compounds do not combine with one another automatically, nor do chemical compounds break apart automatically. The great majority of the chemical reactions that occur within living things must be energized. This means that the atoms of a molecule must be separated by energy put into the system. The energy forces apart the atoms in the molecules and allows the reaction to take place.

To initiate a chemical reaction, a type of "spark," referred to as the energy of activation, is needed. For example, hydrogen and oxygen can combine to form water at room temperature, but the reaction requires activation energy.

Any chemical reaction in which energy is released is called an exergonic reaction. In an exergonic chemical reaction, the products end up with less energy than the reactants. Other chemical reactions are endergonic reactions. In endergonic reactions, energy is obtained and trapped from the environment. The products of endergonic reactions have more energy than the reactants taking part in the chemical reaction. For example, plants carry out the process of photosynthesis in which they trap energy from the sun to form carbohydrates.

The activation energy needed to spark an exergonic or endergonic reaction can be heat energy or chemical energy. Reactions that require activation energy can also proceed in the presence of biological catalysts. Catalysts are substances that speed up chemical reactions but remain unchanged themselves. Catalysts work by lowering the required amount of activation energy for the chemical reaction. For example, hydrogen and oxygen combine with one another in the presence of platinum. In this case, platinum is the catalyst. In biological systems, the most common catalysts are protein molecules called enzymes. Enzymes are absolutely essential if chemical reactions are to occur in cells.


Enzymes

The chemical reactions in all cells of living things operate in the presence of biological catalysts called enzymes. Because a particular enzyme catalyzes only one reaction, there are thousands of different enzymes in a cell catalyzing thousands of different chemical reactions. The substance changed or acted on by an enzyme is its substrate. The products of a chemical reaction catalyzed by an enzyme are end products.

All enzymes are composed of proteins. (Proteins are chains of amino acids.) When an enzyme functions, a key portion of the enzyme called the active site interacts with the substrate. The active site closely matches the molecular configuration of the substrate. After this interaction has taken place, a change in shape in the active site places a physical stress on the substrate. This physical stress aids the alteration of the substrate and produces the end products. During the time the active site is associated with the substrate, the combination is referred to as the enzyme-substrate complex. After the enzyme has performed its work, the product or products drift away. The enzyme is then free to function in another chemical reaction.

Enzyme-catalyzed reactions occur extremely fast. They happen about a million times faster than uncatalyzed reactions. With some exceptions, the names of enzymes end in "-ase." For example, the enzyme that breaks down hydrogen peroxide to water and hydrogen is catalase. Other enzymes include amylase, hydrolase, peptidase, and kinase.

The rate of an enzyme-catalyzed reaction depends on a number of factors, such as the concentration of the substrate, the acidity and temperature of the environment, and the presence of other chemicals. At higher temperatures, enzyme reactions occur more rapidly, but only up to a point. Because enzymes are proteins, excessive amounts of heat can change their structures, rendering them inactive. An enzyme altered by heat is said to be denatured.

Enzymes work together in metabolic pathways. A metabolic pathway is a sequence of chemical reactions occurring in a cell. A single enzyme-catalyzed reaction may be one of multiple reactions in a metabolic pathway. Metabolic pathways may be of two general types: catabolic and anabolic. Catabolic pathways involve the breakdown or digestion of large, complex molecules. The general term for this process is catabolism. Anabolic pathways involve the synthesis of large molecules, generally by joining smaller molecules together. The general term for this process is anabolism.

Many enzymes are assisted by chemical substances called cofactors. Cofactors may be ions or molecules associated with an enzyme and required in order for a chemical reaction to take place. Ions that might operate as cofactors include those of iron, manganese, and zinc. Organic molecules acting as cofactors are referred to as coenzymes. Examples of coenzymes are NAD and FAD.



Adenosine Triphosphate (ATP)

The chemical substance that serves as the currency of energy in a cell is adenosine triphosphate (ATP). ATP is referred to as currency because it can be "spent" in order to make chemical reactions occur. The more energy required for a chemical reaction, the more ATP molecules must be spent.

Virtually all forms of life use ATP, a nearly universal molecule of energy transfer. The energy released during catabolic reactions is stored in ATP molecules. In addition, the energy trapped in anabolic reactions (such as photosynthesis) is trapped in ATP molecules.

An ATP molecule consists of three parts. One part is a double ring of carbon and nitrogen atoms called adenine. Attached to the adenine molecule is a small five-carbon carbohydrate called ribose. Attached to the ribose molecule are three phosphate units linked together by covalent bonds.

The covalent bonds that unite the phosphate units in ATP are high-energy bonds. When an ATP molecule is broken down by an enzyme, the third (terminal) phosphate unit is released as a phosphate group, which is an ion. When this happens, approximately 7.3 kilocalories of energy are released. (A kilocalorie equals 1,000 calories.) This energy is made available to do the work of the cell.

The adenosine triphosphatase enzyme accomplishes the breakdown of an ATP molecule. The products of ATP breakdown are adenosine diphosphate (ADP) and a phosphate ion. Adenosine diphosphate and the phosphate ion can be reconstituted to form ATP, much like a battery can be recharged. To accomplish this, synthesis energy must be available. This energy can be made available in the cell through two extremely important processes: photosynthesis and cellular respiration.



ATP Production

ATP is generated from ADP and phosphate ions by a complex set of processes occurring in the cell. These processes depend on the activities of a special group of cofactors called coenzymes. Three important coenzymes are: nicotinamide adenine dinucleotide (NAD); nicotinamide adenine dinucleotide phosphate (NADP); and flavin adenine dinucleotide (FAD).

Both NAD and NADP are structurally similar to ATP. Both molecules have a nitrogen-containing ring called nicotinic acid, which is the chemically active part of the coenzymes. In FAD, the chemically active portion is the flavin group. The vitamin riboflavin is used in the body to produce this flavin group.

All coenzymes perform essentially the same work. During the chemical reactions of metabolism, coenzymes accept electrons and pass them on to other coenzymes or other molecules. The removal of electrons or protons from a coenzyme is oxidation. The addition of electrons to a molecule is reduction. Therefore, the chemical reactions performed by coenzymes are called oxidation-reduction reactions.

The oxidation-reduction reactions performed by the coenzymes and other molecules are essential to the energy metabolism of the cell. Other molecules participating in this energy reaction are called cytochromes. Together with the coenzymes, cytochromes accept and release electrons in a system referred to as the electron transport system. The passage of energy-rich electrons among cytochromes and coenzymes drains the energy from the electrons to form ATP from ADP and phosphate ions.

The actual formation of ATP molecules requires a complex process referred to as chemiosmosis. Chemiosmosis involves the creation of a steep proton (hydrogen ion) gradient. This gradient occurs between the membrane-bound compartments of the mitochondria of all cells and the chloroplasts of plant cells. A gradient is formed when large numbers of protons (hydrogen ions) are pumped into the membrane-bound compartments of the mitochondria. The protons build up dramatically within the compartment, finally reaching an enormous number. The energy released from the electrons during the electron transport system pumps the protons.

After large numbers of protons have gathered within the compartments of mitochondria and chloroplasts, they suddenly reverse their directions and escape back across the membranes and out of the compartments. The escaping protons release their energy in this motion. This energy is used by enzymes to unite ADP with phosphate ions to form ATP. The energy is trapped in the high-energy bond of ATP by this process, and the ATP molecules are made available to perform cell work. The movement of protons is chemiosmosis because it is a movement of chemicals (in this case protons) across a semipermeable membrane. Because chemiosmosis occurs in mitochondria and chloroplasts, these organelles play an essential role in the cell's energy metabolism.