Chapter 8 - Energy and Enzymes: An Introduction to Metabolism
Termini in questo insieme (40)
What are metabolic pathways?
An ordered series of chemical reactions that build up or break down molecules
EX: A substrate binds to an enzyme & reacts → products are released → products bind to a new enzyme → new products (process repeats)
Until feedback inhibition
What is feedback inhibition?
When the final product of a series of chemical reactions shuts down an earlier enzyme, preventing further production of that product.
What are the two types of energy in chemical reactions?
Kinetic energy (Thermal Energy) - energy of motion
Potential energy (Chemical Energy) - energy stored in position or configuration
What type of bonds have high potential energy? Low potential energy?
Longer, weaker bonds with equally shared electrons (non-polar)
Shorter, stronger bonds with unequally shared electrons (polar)
What does the amount of potential energy in covalent bonds reflect?
Position of shared electrons
What are the laws of thermodynamics? Describe each.
Energy is conserved; it cannot be created or destroyed, only transferred or transformed
Total energy always increases in a system
What is enthalpy?
The total energy in a molecule (heat)
What are exothermic reactions? Endothermic reactions? What are their signs?
Heat energy is absorbed; ΔH is positive; products have higher potential energy
Heat energy is released; ΔH is negative; products have lower potential energy than reactants
What is entropy? What does it mean when products are less/more ordered? Sign?
Amount of disorder (randomness)
More ordered = less entropy, less ordered = more entropy
ΔS = change in entrop
What are spontaneous and non-spontaneous reactions? What determines which they are?
Spontaneous - no energy required for reaction
Non-spontaneous - energy input is required for reaction
Gibbs free energy (G)
What is the standard free-energy change equation
ΔG = ΔH - TΔS
ΔG = change in free energy
ΔH = change in enthalpy
ΔS = change in entropy
T = temperature in kelvin
What kind of reaction is spontaneous, nonspontaneous, when ΔG = 0?
Exergonic
Endergonic
Reaction is at equilibrium
What are endergonic reactions? Exergonic?
Gibbs free energy is absorbed
Gibbs free energy is released
What factors increase reaction rate
Higher concentration → more collisions
Higher temperature → higher reaction rate
What is the iodine clock experiment?
Concluded:
Reaction rate increased when the temperature of the reaction mixture was higher
Reaction rates higher when reaction concentrations are higher
What is energetic coupling?
Between endergonic and exergonic reactions; when the release of chemical energy from an exergonic reaction powers an endergonic reaction
Energy can be transferred through electrons or transfer of a phosphate group
How do redox reactions and energetic coupling relate?
Oxidation is loss of electrons, so exergonic
Reduction is gaining electrons, so endergonic
What two ways are electrons gained or lost in redox reactions?
Change in number of electrons in valence shell
Electrons are transferred as new covalent bonds form with other atoms - atom is either reduced or oxidized
From what to what are electrons transferred?
Electron donor → electron acceptor
Acceptors gain potential energy as they are reduced (bc reduction is gaining electrons)
Electrons are accompanied by a proton, so add H’s
Give examples of electron carriers.
FADH2: Flavin adenine dinucleotide (FAD) accepts two electrons + two protons to form FADH2 → has reducing power
NADH: Nicotinamide adenine dinucleotide (NAD+) accepts two electrons plus one proton to form NADH
They readily donate electrons to other molecules
What is ATP?
Energy currency for cells:
Provides fuel for cellular activities
Ribonucleotide used for RNA synthesis
Has a lot of potential (stored) energy - bond between 3 negatively charged phosphate groups
The negative charges repel each other, but are forced together
Describe the hydrolysis reaction of ATP.
Bond between the outermost P group and its neighbor is broken --> becomes ADP (now only 2 phosphate groups)
Highly exergonic reaction (bc losing a P group releases energy)
Raises the temperature of water, 1 kg per 1 degree Celsius
What is released during the hydrolysis reaction of ATP? What is it used for?
7.3 kilocalories of energy per mole of ATP released during the reaction
A kilocalorie raises 1kg of water by 1 degree Celsius
Provide energy for cellular activity
How does ATP hydrolysis provide energy?
ATP reacts w/ H20 & breaks down into ADP & 1 P group -> free energy & H2O
Phosphate Transfer: P group transferred from 1 molecule to another, changing receiving molecule & helps drive energy-requiring rxn.
Electron transfer: e- are transferred from 1 molecule to another-redox rxn.
What is phosphorylation? How does it impact potential energy & relate to energetic coupling?
The process of adding a P group to a molecule.
Potential E: Adding a P group can increase a molecule’s potential energy, making it more reactive.
Energetic coupling: Cells use energy released from ATP hydrolysis to transfer a P group to another molecule. This helps drive reactions that need energy.
What is activation energy? Transition state?
Activation energy: The minimum energy needed to start a chemical reaction.
Transition state: The unstable, high-free-energy state that molecules pass through as bonds are breaking and forming during a reaction
What is required of the reactants for a reaction to take place?
Must collide in a PRECISE orientation
Have enough kinetic energy to overcome activation energy barrier & achieve transition state
What are enzymes? How do they make reactions more likely
Catalysts that bring reactants together in more precise orientations
By decreasing activation energy required for reaction to proceed
What are reactants called when they bind to an enzyme? Where specifically do they bind?
Substrate
Active site
What is a conformational change?
A change in a protein’s shape that affects how it works.
An enzyme changes shape when a substrate binds to it, helping the enzyme carry out a reaction.
Called an “induced fit”
What holds the substrate in place in the active site?
Hydrogen bonding
Weak amino acid residue interactions
What are the three steps to enzyme catalysis? Describe each.
Initiation - substrates precisely oriented as they bind to active site
Transition state facilitation - interaction between substrate and active site R-groups lowers activation energy
Termination - reaction products are released from enzyme
What limits the rate of catalysis
Decrease with high concentrations of substrate - “saturation kinetics”
Increase at low substrate concentrations
What molecules help enzyme functionality?
Cofactors - inorganic ions that help enzymes work by reversibly reacting with it - Zn+2, Fe+2
Coenzymes - organic molecules that carry e- or chemical grps to the enzyme - NADH, FADH2
Prosthetic grps - non-amino acid atoms or molecules permanently attached to proteins
Ex - prosthetic leg
What factors affect enzyme activity?
Temperature
pH
Interactions with other molecules
Modification of primary structure
What are regulatory molecules?
Molecules that regulate cells' enzymatic activity
Can change enzyme structure, change ability to bind to its substrate, or activate/inactivate the enzyme
What is competitive inhibition? Allosteric inhibition?
Molecule competes with the substrate for the active site
Molecule binds at a location other than the active site → causes a change in the shape of the enzyme, deactivating or activating it
What are catabolic pathways? Anabolic pathways?
Break down molecules into sources of energy and carbon building blocks
Use energy and carbon building blocks to synthesize molecules
What is covalent modification, and why is phosphorylation the key example?
The cell attaches a small chemical grp to an enzyme via covalent bond, altering its primary structure--either irreversible (peptide bond cleavage) or reversible
Phosphorylation = the most common reversible. The phosphate's charges shift a loop, changing the enzyme's shape & flipping it ON or OFF
What is a peptide bond cleavage?
When the link between two amino acids gets cut, splitting the protein chain — and it can't be undone on its own.