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Energy + Enzymes & Cellular Respiration + Fermentation
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Kinetic Energy
energy of motion
Potential Energy
energy that is stored in position or configuration (different forms: gravitational, electrical, chemical)
1st law of thermodynamics
energy is conserved; not created nor destroyed, only transferred or transformed
enthalpy
total ENERGY of a molecule
exothermic
when a reaction releases heat (change in enthalpy)
endothermic
when a reaction takes up heat (change in enthalpy)
2nd law of thermodynamics
total entropy in a system always increases
entropy
amount of disorder in a system
exergonic
SPONTANEOUS chemical reaction (releases energy)
endergonic
non-spontaneous (requires energy)
temp vs reaction rule
when temperature is high, reactions collide more, increasing reaction rate
concentration vs reaction rate
when concentration is high, reactants collide more, increasing reaction rate
energetic coupling
exergonic + endergonic reactions pair, transfer free energy from one reaction to another through electron/phosphate transfer
reduction-oxidation reactions (redox)
reactions that involve the loss or gain of electrons (2 half reactions that occur as a pair)
oxidation
the loss of electrons (spontaneous and exergonic)
reduction
the gain of electrons (nonspontaneous and endergonic)
electrons can be gained or lost in what two ways?
change in the # of electrons in the valence shell
transferred as new covalent bonds are formed w/ other atoms
electron donor
molecule giving up an electron
electron acceptor
molecule receiving electron (most electron donors GAIN potential energy)
flavine adenine dinucleotide (FAD)
cellular electron acceptor that is reduced by 2 electrons and gains 2 protons to form FADH2
nicotinamide adenine dinucleotide (NAD+)
reduced to form NADH (2 electrons reduce NAD+ and it gains 1 proton)
adenine triphosphate (ATP)
ribonucleotide for RNA synthesis
phosphorylation
addition of a phosphate group to a molecule (when ATP is a phosphate donor, phosphorylation is exergonic!)
activation energy
minimum amount of kinetic energy required even in spontaneous reactions (required to sufficiently strain chemical bonds and form products)
transition state
intermediate point between breaking old bonds and forming new ones (free energy of this state is high because old bonds must be destabilized, when products form free energy drops sharply)
What must happen before any chemical reactions can take place?
reactants must collide in a precise orientation
reactants must have enough kinetic energy to overcome the activation energy barrier + acheive the transition state
substrates
reactants that undergo a chemical reaction by binding to an enzyme
enzymes are catalysts:
bring substrates together in a precise orientation that makes reactions more likely to occur
enzymes lower activation energy but aren’t consumed in a chemical reaction
active site
where enzymes bring substrates together to collide
enzymes undergo a conformational/shape change when a substrate binds to an active site
induced fit = enzyme changing shape when a substrate binds
Steps for enzymes catalyzing reactions:
Initiation = enzymes orient substrates as they bind to the active site
Transition State Facilitation = catalyst’s active site lets transition state reaction occur much more actively
Termination = reaction products have less affinity for active site, products are released, enzyme returns to OG conformation
Cofactors
Enzyme helpers; inorganic ions such as metal ions, that reversibly interact with enzyme
Coenzymes
organic molecules that reversibly interact with enzymes, such as electron carrier
Prosthetic Groups
atoms or non-amino acid molecules that are permanently attached to proteins such as pigments
molecule retinal
involved in converting light energy into nerve impulses
Why does ATP have such high potential energy?
the negatively charged phosphate groups creates an instability making the bonds between them high-energy bonds that store significant energy
What happens when glucose is oxidized?
Much of the potential energy stored in the glucose’s chemical bonds is converted into kinetic energy in the form of heat and light
Glycolysis
one six-carbon molecule of glucose is broken down into two molecules of the three-carbon compound pyruvate
starting molecule: 1 glucose (C6H12O6)
CO2 produced: 0
ATP produced: 4 total, 2 NET
FADH2 produced: 0
NADH produced: 2
ending molecule: 2 pyruvate (C3H3O3)
Pyruvate Processing
each pyruvate produced by glycolysis is processed to release one molecule of CO2 and the remaining 2 carbons are used to form the compound CoA — the oxidation of pyruvate results in more NAD+ being reduced to NADH
starting molecule: 2 pyruvate (C3H3O3)
CO2 produced: 2
ATP produced: 0
FADH2 produced: 0
NADH produced: 2
ending molecule: 2 acetylCoA
Citric Acid Cycle (Kreb’s Cycle)
the 2 carbons from each acetylCoA produced by pyruvate processing are oxidized to 2 molecules of CO2 — during this sequence of reactions, more ATP and NADH are produced, and FAD is reduced to FADH2
starting molecule: 2 acetylCoA
CO2 produced: 4
ATP produced: 2
FADH2 produced: 2
NADH produced: 6
ending molecule: oxaloacetate
Electron Transport + Oxidative Phosphorylation
electrons from the NADH and FADH2 produced by pyruvate processing and the citric acid cycle move through a series of electron carriers that together are called the elctron transport chain — the energy obtained from this chain of redox reactions is used to create a proton gradient across a membrane; ensuring the flow of protons back across the membrane is used to make ATP — because this mode of ATP production links oxidation of NADH and FADH2 with phosphorylation of ADP, it is called oxidative phosphorylation
starting molecule: 10 NADH, 2 FADH2
CO2 produced: 0
ATP produced: 30 - 38
FADH2 produced: 0
NADH produced: 0
ending molecule: NAD+, FAD, H2O, and ATP
cellular respiration
defined as any set of reactions that uses electrons harvested from high energy molecules to produce ATP via the electron transport chain
catabolic pathways
sets of reactions that BREAKDOWN molecules
anabolic pathways
sets of reactions that SYNTHESIZE to larger molecules
Glycolysis Process
glycolysis starts by using ATP, not producing it
glucose is phosphorylated to form glucose-6-phosphate
2nd reaction rearranges to fructose-6-phosphate
3rd reaction adds a 2nd phosphate group forming fructose
energy payoff, consists of exergonic reactions that don’t require energy
6th reaction forms 1st high energy molecules: where 2 NAD+ molecules are reduced to NADH
In reactions 7 + 10, enzymes catalyze the transfer of a phosphate group forming a phosphorylated substrate to ADP, forming ATP (substrate level phosphorylation)
for each molecule of glucose processed by glycolysis, the NET yield is 2 molecules of NADH, 2 of ATP, and 2 pyruvate
substrate level phosphorylation
direct enzymatic transfer of a phosphate group from a high-energy substrate molecule to ADP, producing ATP without the help of the ETC
phosphofructokinase
key glycotic enzyme that catalyzes the synthesis of fructose-1,6-biphosphate from fructose-6-phosphate
mitochondrial matrix
compartment enclosed in the inner membrane
cristae = sac-like compartments formed when portions of the inner membrane protrude into the interior of the organelle and expand
Pyruvate Processing Process
pyruvate moves from cytosol across mitrochondrial outer membrane, then transported into matrix via a carrier protein in the inner membrane (prokaryotes don’t have mitochondria, a similar process occurs in the cytosol)
pyruvate dehydrogenase couples the oxidation of one carbon in pyruvate to the reduction of a CO2 molecule + production of NADH (CO2 is released and CoA is added)
acetyl-CoA is produced, 2 NADH and 2 CO2 are produced
Citric Acid Cycle / Krebs Cycle Process
cycle starts with citrate (C6H5O7)
energy harvested by oxidizing the acetyl-group
substrate level phosphorylation
generates 6 molecules of NADH, 2 FADH2, 2 ATP, and 4 CO2
produces the molecules oxaloacetate
Electron Transport Chain Process
oxidative phosphorylation
starts off with 10 NADH and 2 FADH2
components of ETC are organized into 4 large complexes of proteins, complexes 1-11 and protein cytochrome (cyt-c) act as shuttles that transfer electrons between complexes
oxidative phosphorylation oxidizes CO2, FADH2, and NADH — oxidizing them to NAD+, FAD, H2O
oxidative phosphorylation’s main role is to produce ATP, it produces 30-38 ATP
final products = NAD+, FAD, H2O, and ATP
ubiquinoe
pool of nonprotein molecules in the inner membrane of the mitochondrion, belonging to a family of compounds called quinoes (also referred to as coenzyme Q!) = lipid soluable and moves efficiently throughout the hydrophobic interior of the inner mitochondrial membrane
redox potential
an electron acceptor’s ability to accept electrons in a redox reaction
some molecules gain a proton with each electron, forming bonds to uncharged hydrogen atoms — some only gain electrons
Coenzyme Q and ETC differ in redox potential, so it should be possible to arrange their redox reactions to a logical sequence (electrons will pass from molecules w/ lower redox potential to one with higher redox potential — the potential energy in each successive bond in ETC would lessen)
role of ETC
generates electron carriers NADH + FADH2, which are needed for glycolysis as well as generating a proton gradient across the mitochondrial inner membrane that powers the synthesis of ATP
ATP synthase
the entire protein complex is known as this — the stalks + knobs of vesicles synthesize ATP + hydrolyze it to form ADP and inorganic phosphate (when knobs were not present the vesicles could not make ATP, but could transport proteins across membrane)
Chemiosmosis Hypothesis
proposed ETC only purpose is to pump proteins across inner membrane of mitochondria from matrix to intermembrane space, after proton gradient was established an inner membrane enzyme will synthesize ATP from ADP and Pi
proton-motive force
powers production of ATP outside of the vesicle using a proton gradient alone, in the absence of ETC created by the proton pumping activity of the ETC
oxidative phosphorylation
as the shaft spins w/ the knob unit, it is thought to change the shape of the knob subunits in a way that catalyzes the phosphorylation of ADP to ATP
where does the energy for oxidative phosphorylation come from?
comes from an established proton gradient, not phosphorylated substrates as used in substarte level phosphorylation
aerobic respiration
processes used by species that depend on oxygen as an electron acceptor for the ETC for cellular respiration (most efficient)
anaerobic respiration
cells that depend on ETC w/ electron acceptors other than oxygen for cellular respiration
fermentation
metabolic pathway that includes glycolysis and an additional set of reactions that oxidize stockpiles of NADH to regenerate NAD+
in respiring cells, fermentation serves as an emergency backup so that glycolysis can continue to produce ATP even when ETC + oxidative phosphorylation is shut down
lactic acid fermentation
regenerates NAD+ by reducing pyruvate to form lactate — a deprotonated form of lactic acid
produced when there is little to no oxygen in muscles, this receives ETC and lactic acid fermentation can convert back to pyruvate and be used as a source of energy to continue cellular respiration
alcohol fermentation
occurs in the eukaryote Saccharomyces Cerevisiae, strains of which make bakers + brewers yeast
1st convert pyruvate to the 2 carbon compound acetaldehyde, giving off CO2
acetaldehyde accepts electrons from NADH, forming NAD+ required to keep glycolysis going, this forms ethanol as a waste product
obligate anaerobes
bacteria + archaea that rely exclusively on fermentation
why is fermentation considered inefficient compared to cellular respiration?
fermentation produces just 2 ATP per glucose metabolized, while cellular respiration produces about 29 ATP
facultative anaerobes
organisms that can switch between fermentation and aerobic cellular respiration
many human cells function as facultative anaerobes to a certain extent, but we can’t survive for long without oxygen
dehydrogenase
removed a pair of hydrogens
kinase
adds a phosphate group
phosphotase
removes a phosphate group
isomerase
moves atoms around, making isomers but keeping the same molecular formula (ex: turning glucose into fructose)