Unit 4: Chapter 20 Flashcards
In eukaryotic cells, vast majority of ATP synthesis is from _____ _______
oxidative phosphorylation
Electron Transport Chain
- Transfers high energy electrons donated by reduced electron carriers NADH and FADH2 to oxygen and also generates proton gradient within mitochondria
- Series of oxidation reduction reactions
Cellular respiration
Collectively, citric acid cycle and oxidative phosphorylation
Intermembrane space
Space between outer and inner membrane of mitochondria
Proton pumps protons from ____ to ______ ______
matrix; intermembrane space
Where does ETC and ATP synthase occurs?
Inner mitochondrial membrane
Redox potential (E0)
Measures of a molecule’s tendency to donate or accept electrons
Where does citric acid cycle and fatty acid oxidation occur?
matrix
Electron transfer potential of an electron is measured as ____ _____
redox potential
Negative Reduction potential (E0) indicates
Strong reducing agent
Readily donates electrons
Positive Reduction potential (E0) indicates
Strong oxidizing agent
Readily accept electrons
Electrons move from more _____ to ______
negative reduction potential (reduced) to more positive reduction potential (oxidized)
The energy released when high energy electrons are transfered create a ____
proton gradient
If E0’ for an oxidation reduction is positive, will ΔG°’ be positive or negative?
Negative
The final electron acceptor is the most positive ____
Positive reduction potential (E0)
Oxygen is final electron acceptor because it has …
most positive value of reduction potential (E0)
ETC is composed of
4 large protein complexes
Electrons donated by NADH and FADH2 are passed through ____ in ____
electron carriers ; protein complexes
Electron carriers in ETC that are proton pumps include
flavin mononucleotide (FMN), iron sulfur proteins, cytochromes, and coenzyme Q
Coenzyme A, FAD,NAD, NADPH all have common structure of
ADP
Flavin mononucleotide (FMN) does not have ____ in its structure
ADP
Iron Sulfur Clusters
- cystine and disulfide bonds
- help transport electrons through the ETC & provide structural support.
- can undergo oxidation and reduction reactions
Flow of electron carriers of ETC
NADH –> FADH2 –> ubiquinone –> cytochrome –> O2
Flowing from most negative reduction potential to most positive reduction potential
What complexes contain iron sulfur clusters
Complex I, II, III
Cytochrome structure
Heme group with varrying side chains
Iron
All cytochromes contain
heme groups
Coenzyme Q (ubiquinone)
- Derived from isoprene
- Transfer only one electron at a time
- Binds protons (QH2) and electrons
- Can exist in several oxidation states
Coenzyme Q (ubiquinone) can transfer one electron at a time through a stable _____
semiquinone
Transfer electron process of Coenzyme Q
Odizied form of coenzyme Q (Q, ubiquinone) accepts one electron
–>Semiquinone intermediate (QH*) accepts one electron –> Reduced form of coenzyme Q (QH2, ubiquinol)
Coenzyme Q (ubiquinone) can receive total ___ but can only transfer ___
2 electrons ; 1 electron
What complex is not a proton pump?
Complex II
What complexes are proton pumps?
Complex I, III, IV
Electron flow from NADH to O2 go through complex:
I –> III –> IV in inner mitochondrial membrane
Electrons flow from FADH to O2 through complex:
II –> III –> IV in inner mitochondrial membrane
Complexes that are proton pumps, pump protons from _____ to ____ to generate proton gradient
mitochondrial matrix ; intermembrane space
NADH Q Oxidoreductase (complex I)
Prosthetic group:
FMN
FeS
Succinate Q reductase (complex II)
Prosthetic group:
FAD
FeS
Q- cytochrome C oxidoreductase (complex III)
Prosthetic group
Heme BH
Heme B1
Heme C1
FeS
Cytochrome C oxidase (complex IV)
Prosthetic group:
Heme a
Heme a3
CuA
CuB
If start from acetyl CoA: how many NADH and elecrons enter ETC
3 NADH
6 e-
If start from pyruvate: how many NADH and elecrons enter ETC
4 NADH
8 e-
NADH Q Oxidoreductase (complex I)
- High potential electrons of NADH are oxidized
- Conezyme Q is reduced to Q to QH2
- QH2 leaves enzyme for Q pool
- proton pump for 4 protons pumped out
NADH drops 2 electrons to FMN –> FeS –> Coenzyme Q
NADH –> NAD+
WHat complex of ETC oxidizes NADH, reduces coenzyme Q and pumps protons?
Complex I
Reaction equation for NADH Q Oxidoreductase (complex I)
NADH + Q + 5 H+matrix –> NAD+ + QH2 + 4H+intermembrane space
Sum of Steps in NADH Q Oxidoreductase (complex I)
Step 1: Transfer of e- from NADH to flavoprotein
Step 2: Reduced FMN is reoxidized and oxidized form of iron sulfur protein is reduced
Step 3: Reduced ion sulfur proteins donates its electron to Coenzyme Q to create QH2
Succinate Q reductase (complex II)
- entry point for FADH2
- FADH2 reduces iron sulfur protein which then reduces Q to QH2 and QH2 enters Q pool
- succinate dehydrogenase in TCA
What enzyme from the citric acid cycle is part of complex II?
Succinate dehydrogenase
(reminder: not found in matrix but embedded in inner mitochondrial membrane
Reaction equation for succinate Q reductase (complex II)
succinate + CoQ –> Furmate + CoQH2
ΔG°= -13.5 kJ/mol
Succinate Q reductase (complex II) ΔG°= -13.5 kJ/mol is significant because
not enough energy to drive ATP production
QH2 carries ___ while cytochrome C carries ___
2 electrons, 1 electron
Q Cycle
Mechanism for coupling in one cycle
In one Q cycle, ___ are pumped out of mitochondria and __ more are removed from matrix
4 protons, two protons
What provides the link betwween two electron transfers (NADH and FADH2) and one electron transfers (cytochromes)?
Q cycle
The Q cycle is dependent on
coenzyme Q can exist in 3 forms so one electron transfer at a time is possible
Cytochrome
all contain heme group with varying side chains
In heme group, iron is reduced to Fe3+ and reoxidized to Fe2+
How are diferent types of cytochrome distinguished by
Lowerclase letters (a, b, c) and further distinction with subscripts
Q cytochrome C oxidoreductase (complex III)
- proton pump
- electrons from QH2 are used to reduce 2 molecules of cytochrome c
- includes 2 b type cytochromes (bh and bc), cytochrome c1, and iron sulfur proteins
Reaction equation for Q cytochrome C oxidoreductase (complex III)
QH2 + 2CytCox + 2H+matrix –> ! + 2CytCred + 4H+intermembrane space
__ of cytochrome c are required for every molecule of coenzyme Q in complex III
2 molecules
Cytochrome C
- Small mobile peripheral protein in inner mitochondrial membrane
- Shuttles electrons between complex III and IV
- Very conserved across all living systems
Cytochrome C oxidase (complex IV)
- proton pump
- accepts 4 electrons from 4 molecules of cytochrome C in order to catalyze reduction of O2 to 2H20
- 2H+ pumped out to reduce 1 H20
The 8 protons that are removed from the protons from complex IV are used for
4 molecules are chemical protons used to reduce oxygen
4 protons are pumped into intermembrane space
Reaction equation of Cytochrome C oxidase (complex IV)
4 CytCred + 8H+matrix –> 4 CytCox + 2h20 + 4H+ intermembrane space
Inhibitors of ETC
Roteone Amytal: inhibits complex I
Antimycin A: inhibits complex III
Cyanide, Carbon Monoxide, Azide: Inhibits complex IV