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metabolism
teh totality of an organism’s chemical reactions
catabolic pathway
metabolic pathway that breaks down larger molecules into simpler molecules and releases energy
anabolic pathway
metabolic pathway that builds larger molecules out of simpler molecules and require energy
what kind of energy is chemical
potential
what kind of energy is thermal
kinetic
1st law of thermodynamics
energy can be transferred or transformed but it cannot be created nor destroyed
2nd law of thermodynamics
every energy transfer or transformation increases the entropy of the universe
heat lost to environment → increase
breaking molecules → increase
decrease → requires external energy
spontaneous reactions
reactions that increase entropy will occur spontaneously, which is energetically favorable
free energy
G; the energy available to perform work when pressure and temperature and constant; ∆G = ∆H - T∆S where H=enthalpy, and S=entropy; a measure of how far a system is from equilibrium; does NOT give info about speed at which a process occurs
∆G<0
reaction is exergonic and spontaneous
∆G>0
reaction is endergonic and not spontaneous
∆G = 0
equilibrium
endergonic reaction
requires energy
exergonic reaction
realeases energy
exergonic and endergonic reaction coupling
an endergonic reaction can only proceed if it’s coupled with an exergonic reaction with a greater amount of ∆G; ex: ATP hydrolysis (ex) is coupled with (en) reactions
transition state
unstable species that exists half way between the products and reactants of a reaction
activation energy
E_A; the difference in G between the reactants and the transition state; determines reaction rate; the higher th E_A, the slower the reaction
catalyst
accelerates reactions by lowering their E_A; not consumed by reactions they accelerate
enzymes
catalysts of life; accelerate reactions by stabilizing the transition state → lowering the E_A; usually proteins and sometimes RNA
active site
microenvironment created by enzymes to bind their substrates (reactants) and stabilize their transition state; specialized for different substrates; holds substrates and contorts them to resemble the transition state
induced fit
binding of the substrate causes a shape change that forms the active site and activates the enzyme; will not occur if a differently shaped molecule tries to bind; ex: hexokinase changes shape upon binding to glucose, forming active site and preventing water from accessing it and disrupting the reaction
catalytic cycle
substrates enter active site
enzyme arranges them to resemble the transition state; may interact via non-covalent interactions to stabilize the shape; might exclude potentially interfering molecules
the active site lowers E_A
interconversion between products and reactants is accelerated
the enzyme does not bind as tightly to the products as it does the substrates so it releases the products and not the substrates
the enzyme is regenerated so it can catalyze again
competitive inhibitor
resemble the substrate and block access to the active site; can be overcome by increasing substrate concentration; ex: penicilin inhibits the enzyme that is important for bacterial cell wall synthesis
noncompetitive inhibitor
binds elsewhere on the enzyme from the active site and changes its shape; cannot be overcome by increasing substrate concentration; ex: hydrogen cyanide inhibits a mitochondrial enzyme required for ATP synthesis
allostery
the regulation of a process by the binding of a molecule far from where that process occurs
allosteric regulators
molecules that cause the shape change in enzymes causing them to be more or less active (activators or inhibitors); often metabolic products upstream or downstream in the metabolic pathway of the reaction catalyzed by an enzyme
cooperativity
for enzymes with multiple subunits; substrate binding causes a shape change in one subunit and it’s communicated to other subunits
positive → shape change in one subunit encourages the same change in other subunits
negative → shape change in one subunit discourages the same change in other subunits
feedback inhibition
downstream metabolite accumulates and it binds to an enzyme and allosterically or competitively inhibits it
feedforward activation
upstream metabolite accumulates and it binds to an enzyme and allosterically activates it
oxidation
loss of electrons; LEO; exergonic product will have lower ∆G
reduction
gaining ellectrons; GER; endergonic product will have higher ∆G
reducing agent
a substance that loses electrosn and becomes oxidized
oxidizing agent
a substance that gains electrons and is reduced
oxidation and reduction coupling
reduction (unfavorable) can be powered by being paired with oxidation (favorable)
electrons in redox reactions
electrons have greater PE in less electronegative atoms → electrons lose or make available energy when they transfer to more electronegative atoms;
carbon oxidation
carbon can partially lose electrons; the more bonds a less electronegative atom shares with more electronegative atoms, the more oxidized it becomes; carbon oxidation releases energy, so much so that cellular respiration has to break it up into ordered steps to harvest it
glycolysis investment phase
1 molecule of ATP is used to phosphorylate and isomerize glucose into fructose and another is used to phosphorylate that fructose and break it into 1G3P and 1DHAP, which is isomerized into another G3P
overall, per glucose, 2 ATP are used and 2 G3P are produced
glycolysis payoff phase
1 NAD+ is reduced to 1 NADH to harvest electrons
1ATP are generated through substrate phosphorylation after addition of 1 inorganic phosphate
another high energy intermediate powers more substrate-level phosphorylation → 1 more ATP, losing 1 H2O to become that intermediate
these are all per single G3P molecule
overall, per glucose, 4ATP are generated, 2 H2O are created, 2 NAD+ are reduced to NADH and the G3P become 2 pyruvate
substrate-level phosphorylation
metabolic process that produces ATP by directly transferring an inorganic phosphate from a high energy intermediate to ADP
NAD+ and FAD+
modified RNA molecules and electron carriers because electrons lose little energy when transferred fro carbon to them and they can pass electrons to more electronegative atoms to release energy
high-energy intermediate
removal of its phosphate can power ATP synthesis (ADP → ATP); exs:1,3-BPG and PEP
glycolysis overall
purpose is to oxidize 1 glucose (6C) to produce 2 pyruvate (3C each)
mechanism to make ATP without O2
4 electrons are harvested - 2 ATP and 2 NADH
occurs in cytoplasm
inputs: 1 glucose, 2 NAD+, 2 ATP, 2 ADP, 2 P_i
outputs: 2 pyruvate, 2 NADH, 2ATP, and 2 H2O
pyruvate oxidation
pyruvate dehydrogenase decarboxylates (removes a carboxyl group as CO2) and oxidizes pyruvate to harvest 2 more electrons (for 2 pyruvate, 1 electorn each) through NAD+ reduction to NADH and H+
pyruvate is turned into an acetyl group which is attached to coenzyme A (CoA) to form acetyl CoA
pyruvate oxidation inputs and outputs per pyruvate
inputs: 1 pyruvate, 1 NAD+, 1 CoA
outputs: 1 acetyl-CoA, 1 CO2, 1 NADH, 1 H+
ex of coupling reaction in glycolysis
reaction 1: ATP hydrolysis (exergonic) drives an unfavorable reaction (endergonic) forward
ex of structural isomerization in glycolysis
reaction 2: 6-membered ring → 5 membered ring making molecule more reactive for next step
ex of redox and hydration in glycolysis
reaction 6:
redox - NAD+ is reduced to NADH and the carbon on G3P is oxidized
dehydration - phosphate group is added to carbon via dehydration
ex of substrate-level phosphorylation
reaction 7: phosphate group is removed from intermediate and added to ADP
citric acid cycle process
acetyl coA (2C now that 1C lost through CO2) is added to oxaloacetate (4C) to create citrate (6C)
2C from citrate are removed as CO2 and fully oxidized → powers reduction of 3 NAD+ (again per acetyl CoA) (results in NADH and H+) and 1 FAD (results in FADH2) and the synthesis of 1 ATP through substrate-level phosphorylation
The original 4C oxaloacetate is regenerated and reused in the cycle
citric acid cycle overall and inputs/outputs per acetyl coa
turns over twice per molecule of glucose
inputs: 1 acetyl coa, 3 NAD+, 1 FAD, 1 ADP, 1 P_i, 1 oxaloacetate (regenerated)
outputs: 2 CO2, 3 NADH, 3 H+, 1 FADH2, 1 ATP, 1 CoA, 1 oxaloacetate
oxidative phosphorylation electron transport chain
transports electrons while pumping protons from mitochondrial matrix into intermembrane space; FADH2 enters through a different complex from NADH and generates less energy (because its electrons have less PE); oxygen is the final electron acceptor → forms H2O
oxidative phosphorylation chemiosmosis
movement of ions across a sempermeable space (inner mitochondrial membrane) down a concentration gradient to generate ATP; as H+ ions move down gradient, they pass through ATP synthase, which adds P_i to ADP to make ATP
oxidative phosphorylation overall
generates an electrochemical gradient where H+ are concentrated in intermembrane space
makes the most ATP in cellular respiration
cellular respiration overall atp yield
glycolysis - 2
pyruvate oxidation - 0
CAC - 2
oxidative phosphorylation - 26-28
how much energy is harvested from glucose
most of the energy stored in glucose is lost as heat
fermentation
anaerobic metabolic process that microorganisms use to break down glucose into pyruvate into ethanol, lactate, etc.; doesn’t make any additional ATP from glycolysis but does regenerate NAD+
photoautotrophs
organisms that use light as source of energy to synthesize organic substances
open stomata
CO2 is allowed in and water and oxygen is allowed out
closed stomata
no CO2 exchange but no water loss
photosynthesis overall reaction
energy + 6O2 + 6H2O → C6H12O6 + 6O2; carbon in CO2 is reduced; H2O is oxidized; anabolic and endergonic; overall increase in free energy (→ ∆G>0 → endergonic)
photosystem ii purpose
take electrons from water and excite them to a higher energy level
etc 1 purpose
h+ pumps; to generate a H+ gradient to power ATP synthase and move electrons PSI
photosystem i purpose
to excite the electrons further
etc 2 purpose
NADP+ reductase; move high energy electrons to reduce NADP+
photosystem ii output
high energy electrons that are passed to the etc1
etc1 output
h+ gradient established across the thylakoid membrane and electrons passed to psi
photosystem i output
higher energy electrons that are passed etc2
etc 2 output
NADPH which goes to the light-independent reactions
light reactions purpose
transform light energy into chemical energy (ATP) and reducing power (NADPH) to be used by the light independent reactions
pigments
located in the thylakoid membrane of the chloroplast; absorb specific wavelengths of light; major ones are chlorophyll a and chlorophyll b
ps ii process
a photon excites electrons in pigments, which results in energy from the electrons being passed from pigment to pigment until they are passed to the p680 molecules in the reaction center
the energy passed to p680 makes it lose a high-energy electron (oxidizes it) and gives it to the primary electron acceptor
the lost electron is replaced by an electron derived from the splitting of water into 2e-, 2H+ (thylakoid space), and 1O (finds another and makes O2)
P680+
the form P680 takes when it hasn’t regained electrons yet; strongest biological oxidizing agent known
etc 1 process
Pq and Pc carry out redox reactions as electrons flow (are passed from molecule to molecule) down the etc
electron transport releases free energy that is used to pump protons into thylakoid space
proton gradient is generated across thylakoid membrane
chemiosmosis - as H+ ions go back into stroma down concentration gradient, they pass through ATP synthase
ps i process
electron from etc chain arrives at ps i and joins the p700 pair of chlorophylls in the reaction center
light energy is absorbed by pigments and passed inward to the reaction center, causing an electron in P700 to be transferred to an aceptor molecule
the P700 pair’s missing electron is replaced by a new electron from PSII
etc 2 process
the high energy electron is passed down the same kind of chain that ends with NADP+ reductase
NADP+ gets the electron and becomes NADPH
photosynthesis
location
where are H+ concentrated
how is H+ gradient used
source of e-
final electron acceptor
location - chloroplast
H+ concentration location - thylakoid space
H+ gradient used - to make ATP with atp synthase
e- source - water
final electron acceptor - NADP+
cellular respiration
location
where are H+ concentrated
how is H+ gradient used
source of e-
final electron acceptor
location - mitochondrion
H+ located - intermembrane space
H+ gradient used - to make atp with atp synthase
source of e- - NADH, FADH2
final electron acceptor - O2 → H2O
calvin cycle stages
fixation - moving C from an inorganic to organic form
reduction - add e- to C from NADPH
regeneration - remake the molecule needed to accept the CO2
calvin cycle output
g3p
rubisco
enzyme that fixes carbon in the calvin cycle
rubisco * come back with notes