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Chapter 8.1: Metabolism, Energy, and the Laws of Thermodynamics By Richie Kovac What is Metabolism? • Metabolism – the sum of an organism’s chemical reactions. It is an emergent property resulting from interactions between molecules within the environment of the cell. • Metabolic pathway – a series of chemical reactions. It begins with a molecule, is changed through a series of reactions (which are catalyzed by enzymes), and is made into a product. Metabolic pathways in an organism intersect like roads on a map intersect. • Metabolism is like a large map of all the metabolic pathways in an organism. Metabolism: sum of all the metabolic pathways in an organism One street is like a metabolic pathway. The pathways intersect. Example of a metabolic pathway. Molecule A is changed into Molecule F What Does the Metabolism Do? • Manages material and energy resources in a cell • Mechanisms control enzymes that are part of metabolic pathways to either: – a) catalyze a metabolic pathway to produce a certain product if it is in deficiency or – b) to prevent enzymes from catalyzing a reaction, preventing the production of a product (if the product is in excess). Too much of a product inhibits the enzyme involved in making it. As a result, accumulation of the product stops Types of Metabolic Pathways • Catabolic pathways – metabolic pathways that break down complex molecules into simpler Amino Acids compounds, which releases energy form a polypeptide – – Example an example of an anabolic pathway. – cellular respiration Cellular Respirationan example of a catabolic pathway. • Anabolic pathways – pathways that consume energy to build complicated molecules from simpler ones – Example – proteins are built from amino acids. Breakdown Proteins to Amino Acids, Starch to Glucose Synthesis Amino Acids to Proteins, Glucose to Starch Chapter 5 Chapter 5 Chapter 5 Quick Questions • • • • What is Metabolism? What does metabolism do? What are 2 types of metabolic pathways? Which metabolic pathway consumes energy to build complicated molecules from simpler ones? • Using a map as a symbol, what would a road on a map symbolize? Energy • Energy – the capacity to cause change/the ability to rearrange a collection of matter. • Bioenergetics – the study of how energy flows through living systems. • Can be used to perform work – pushing matter against opposing forces. Types of Energy • Kinetic energy – the relative motion of objects – The motion of large or small objects • Heat (thermal energy) – kinetic energy associated with the random movement of atoms or molecules (in a body of matter, the amount of heat is a measure of the matter’s total kinetic energy due to the motion of its molecules). – Has to do with the motion of particles like atoms and molecules • Light • Potential energy – energy that is not kinetic. It is energy that matter possesses because of its location or structure. – Example – water held in a dam above sea level had potential energy. A diver on a diving board has potential energy. • Chemical energy – a form of potential energy, this is energy available in molecules for release in a chemical reaction Potential Energy Quick Questions 2 • • • • • What is energy? What is work? Chemical energy is a type of _____ energy. How are thermal and kinetic energy similar? A cheetah running displays which type of energy in use? Thermodynamics • Thermodynamics – the study of energy transformations that occur in a collection of matter. • “System” – name given to a piece of matter under study. Everything outside the system is known as its “surroundings” • Isolated system – cannot exchange matter or energy with its surroundings. • Open system – can exchange matter or energy with its surroundings. 1st Law of Thermodynamics • Says energy of the universe is constant. Energy can be transferred and transformed, but it cannot be destroyed or created. Matter is conserved – it’s not created or destroyed 2nd Law of Thermodynamics • Says every energy transfer/transformation results in some energy becoming unusable energy. The creation of unusable energy increases the entropy of the universe. • Entropy – a measure of unusable energy within a closed or isolated system. It is also defined as a measure of disorder or randomness. Increased unusable energy in a system, such as the universe, increases chaos in the universe. • To understand the concept of entropy, think of an energy transfer as a class of 20 kids walking from one end of a hallway to another. The kids represent useable energy and their teachers represent systems that use the energy. By the time the kids reach the other end of the hallway, 2 of the 20 kids have turned crazy and chaotic and can no longer be taught (“used”) by the teachers. As the kids move back and forth, eventually all of them will go crazy. 2nd Law of Thermodynamics Continued • This law also states that for a process to occur spontaneously, it must increase the entropy of the universe. • Spontaneous process – one that occurs without the input of energy. Example, a boulder rolling down a hill. The boulder rolls down the hill, releases heat and so increases entropy, and the boulder becomes more stable. • This law permits that the entropy of a particular system may decrease as long as the total entropy of the universe increases. Spontaneous processes, like an uncared office falling apart after a while, increases the entropy of the universe. Final Quick Questions • Can an isolated system exchange energy with its surroundings? • What does the 1st law of thermodynamics say? • What is entropy? • How is entropy related to the 2nd law of thermodynamics? • You’re talking to your friend. He tells you “I performed a chemical reaction today. I ended up with less energy than I started with.” Why is your friend wrong? • Metabolism Animation Free energy change- portion of a system’s energy that can perform work when temperature and pressure are uniform throughout the system The free energy change of a reaction tells us whether or not the reaction occurs spontaneously Symbolized by the letter G • For the professor J. Willard Gibbs, who defined a very useful function called the Gibbs free energy of a system (without considering its surroundings ) in 1878 T his formula is used to determine the free energy change that occurs when a system changes • Example: during a chemical reaction ∆G is the free energy of the system Formula uses only properties of the system (the reaction) itself. ∆H symbolizes the change in system’s enthalpy (in biological systems, this is equivalent to total energy) ∆S is the change in the system’s entropy T is the absolute temperature in Kelvin (K) units ∆G= G final state –G initial state Gfinal state = free energy of the final state of system Ginitial state = free energy of the initial state of the system Spontaneous reactions have a negative ∆G • ∆G<0 • Spontaneous reactions must either give up enthalpy (H must decrease), give up order (TS must increase), or both • This means that every spontaneous process decreases the system’s free energy Processes that have a positive or zero ∆G are never spontaneous Spontaneous does not mean that a reaction will be instantaneous or rapid More free energy (higher G) Less stable Greater work capacity In a spontaneous change: The free energy of the system decreases (∆G <0) The system becomes more stable The released energy can be harnessed to do work Less free energy (lower G) More stable Less work capacity Chemical reactions which proceed downhill, are said to be spontaneous. Spontaneous process may also require energy to overcome an activation barrier. • This means that some processes may be spontaneous, but do not occur at a noticeable rate. Spontaneous reactions occur without outside intervention. They may occur quickly Ex’s: • Combustion of hydrogen • Graphite turning to diamond • Expansion of a gas to fill the volume available to it. • Cooling of a hot object to the temperature of the surroundings According to the second law of thermodynamics, when a spontaneous process occurs, there must be an increase in total entropy. A reaction which cannot occur without the input of work from an external source. ΔG > 0 for nonspontaneous reactions at T and P. Free energy is a measure of a system’s instability Unstable systems (higher G) tend to change in such a way that they become stable (lower G) As a reaction reaches equilibrium, the free energy of the mixture decreases • Conversely, the free energy of the mixture increases when a reaction is somehow pushed away from equilibrium Any change from equilibrium state will have a positive ∆G and will not be spontaneous • For this reason systems never spontaneously move away from equilibrium • Because a system at equilibrium can’t spontaneously change, it can do no work • A process is spontaneous and can perform work only when moving toward equilibrium For a system at equilibrium, G is at its lowest possible value in the system Exergonic reaction- proceeds with a net release of free energy; energy released • Negative ∆G • Occur spontaneously • Example: cellular respiration C6H12O6 + 6O2 → 6CO2 + 6H2O ∆G= -686 kcal/mol (-2870 kJ/mol) Endergonic reaction- absorbs free energy from its surroundings; energy required • Stores free energy in molecules- ∆G is positive • Non-spontaneous • Example: photosynthesis 6CO2 + 6H2O + light energy → C6H12O6 + 6O2 ∆G= 686 kcal/mol •Exergonic- Release energy •Usually occur spontaneously since they do not require energy to occur. •Some exergonic reactions do not occur spontaneously. Instead, they require a small input of energy from some outside source to cause the reaction. This outside energy is called the activation energy of the reaction. •Endergonic - Asorb energy to form bonds •Do not occur spontaneously. •Occur only if energy is available to be used in the reaction. •Endergonic reactions also have an activation energy which is considerably higher than the activation energy for most exergonic reactions. •Many reactions in cells are endergonic, so cells require a method of storing energy until it is needed in a chemical reaction. Is the reaction endothermic or exothermic? This is an exothermic reaction (heat is a product), so heat is released to the surroundings Ellie Quinby Chemical work: The pushing of endergonic reactions that would not occur spontaneously ◦ Ex: synthesis of polymers and monomers Transport work: The pumping of substances across membranes against the direction of spontaneous movement ◦ Ex: proteins through membranes Mechanical work: Movement of the cell itself ◦ Ex: Beating of cilia, contraction of muscle cells Energy coupling: use of an exergonic process to drive and endergonic one (manages cell’s energy use) ATP (adenosine triphosphate) ◦ Contains ribose with nitrogenous base adenine and three phosphate groups bonded to it ◦ Used to make RNA ◦ Breaking it down release more energy then most molecules Hydrolysis◦ Adding water to ATP breaks the molecule into adenosine diphosphate, releasing energy Hydrolysis gets rid of one phosphate and it gets attached to a different molecule Phosphorylation- the molecule that gains the phosphate group is called phosphorylated Regenerated through phosphorylation of ADP Animation Enzymes can denature in heat or extreme pH. ◦ Most enzymes optimal temperature is 98.6, body temperature Many use coenzymes to catalyze reactions Some chemicals inhibit the ability of the enzyme to work ◦ Many are in cells naturally and control metabolism Some reactions require to much energy to begin they are helped by catalysts Activation energy (Free energy of activation): amount of energy needed for a reaction to occur represented by EA Enzymes that act like catalysts decrease the activation energy of a reaction Activation energy barrier- the energy a reaction must absorb to begin- determines rate of reaction Transition State- when a reactions has enough energy to begin, bonds can be broken Heat cannot be used to lower activation energy or it would denature cells’ proteins ◦ Therefore a catalyst must be used Enzymes- catalyze specific reactions in the cells, allowing them to occur quicker Catalyze in the direction of lower change in G( free energy change) Substrate- the reactant and enzyme acts on ◦ The enzyme fits with a specific substrate, and that it what it catalyzes ◦ Forms and enzyme/ substrate complex when together Active site- the area of the enzyme that actually bonds to the substrate Induced fit- when the substrate enter the active site, the enzyme envelops them, allowing a reaction to occur • Enzyme Catalysis Animation Enzyme Animation ENZYMES AND METABOLISM Factors affecting Enzyme Activity Prerna Balasundaram OPTIMAL CONDITIONS • • • • • • Enzymes work better under some conditions than others; this is called optimal conditions. High temperature, increases rate of enzyme reaction allowing each enzyme to have the best activity, however, without it denaturing because of extreme high temperatures. Each enzyme has its own optimal temperature. EXAMPLES - Human enzymes’ optimal temperature – @35 degrees Celsius (close to human temperature). Just like temperature, each enzyme has its optimal pH. EXAMPLES - Most enzyme’s pH 6-8. - The human stomach enzyme, pepsin, works best at pH of 2. COFACTORS AND COENZYMES Cofactors – non protein helpers for catalytic activity that may either be bound tightly to enzyme as permanent residents, or may bind loosely along with substrate; usually are inorganic. EXAMPLES - Zinc, iron, copper Coenzymes – cofactors that are organic. EXAMPLES - Vitamins, raw materials COMPETITIVE & NONCOMPETITIVE INHIBITORS Competitive inhibitors – inhibitors that resemble normal substrates and reduce productivity of enzymes by blocking real substrates from entering active site Noncompetitive inhibitors – do not directly compete with substrate to bind to enzyme at active site; rather they impede enzyme reaction by binding with another part of enzyme EXAMPLE - DDT is a pesticide that inhibits key enzymes in nervous system ALLOSTERIC REGULATION Chemical chaos would result if all of a cell’s metabolic pathways were operating at the same time! Allosteric regulation – any case in which a protein’s function at one site is affected by the binding of a inhibiting regulatory molecule to a separate, regulatory site (sometimes called an allosteric site). Made up by two or more subunits, each composed of a polypeptide chain and having its own active site. COOPERATIVITY & FEEDBACK INHIBITION • • Feedback inhibition – a metabolic pathway is switched off by the inhibitory binding of its end product to an enzyme that acts early in the pathway. EXAMPLE - ATP binds to several enzymes allosterically inhibiting their activity. ADP acts as an activator so if ATP production lags behind ADP activates enzymes and speeds up production, vice versa if ATP production is too high. Cooperativity – one substrate molecule primes an enzyme to accept additional substrate molecules amplifying response of enzymes to substrates EXAMPLE - Oxygen transport of protein hemoglobin REVIEW QUESTIONS What is the optimal temperature and pH for most human enzymes? Give an example of a cofactor and a coenzyme. Compare competitive inhibitors and noncompetitive inhibitors. What is allosteric regulation? Describe how ATP uses feedback inhibition. Enzyme Inhibition Animation Enzyme Specificity Animation