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http://www.illinoisscience.org/event/pi-day-pi-k-fun-runwalk-2/

Outline
Chapter 8
Enzyme review
Chapter 9
Cellular respiration overview
Electrons are transferred by reduction-oxidation
(redox) reactions
Steps in cellular respiration
Glycolysis
Pyruvate oxidation
Citric Acid Cycle
Oxidative phosphorylation (Electron transport chain and
chemiosmosis)

Generating ATP without oxygen

During a laboratory experiment, you discover

that an enzyme-catalyzed reaction has a G of
-20 kcal/mol. If you double the amount of
enzyme in the reaction, what will be the G for
the new reaction?
A) -40 kcal/mol
B) -20 kcal/mol
C) 0 kcal/mol
D) +20 kcal/mol

How can enzymes help to perform

cellular work?

Enzymes
speed up rxns
A spontaneous rxn may take years to occur!
An enzyme itself is not used up in a rxn

are proteins 4 levels of structure

often end in ase

In most reactions
1. Starting molecule must absorb energy
2. Contort to highly unstable shape
(transition state)
3. New bonds form, releasing heat
4. Molecule reforms in stable shape
Activation energy (EA): Energy required to
obtain transition state

Energy barrier
before the rxn
can occur

Fig. 8.13

Enzymes lower the activation energy

Fig. 8.14

Enzymes can regulate chemical reactions

Substrate: what enzyme acts upon
Active site: portion of enzyme that binds to substrate
Pocket or groove that is specific to the shape of the substrate
lock and key

Substrates are held to the enzyme by weak interactions

Fig. 8.15

Fig. 8.16

Enzyme interactions
Small amount of enzyme can have large
effect!
Can catalyze forward or reverse rxn,
depends on which has negative G.
How do enzymes lower EA barrier?

Bending molecules to their transition state

Creating optimal environmental conditions
Holding reactants near each other

 Enzymes have
optimal
conditions for
catalyzing rxns
Rxn rate is
determined by:
Amount of
substrate
Enzyme
speed
Fig. 8.17

Enzyme activity is regulated by activators

and inhibitors
Activators: chemicals that must bind for an enzyme
to be active
Cofactors: non-proteins; also bond to enzyme
Inhibitors: Chemicals that shut off enzyme activity

Competitive Inhibition
A molecule that is structurally similar to the substrate
competes for the active site on the enzyme.

This ties up the enzyme, so that it is not available for

the substrate.
What if the substrate amount is raised, while the
concentration of the inhibitor is held constant?

Noncompetitive inhibition
The inhibitor binds to a site
that is not the active site.
This can change the shape of
the enzyme, so that the active
site no longer fits the
substrate.

Fig. 8.18

Allosteric Regulation: enzyme function at one site

affected by binding somewhere else

Fig. 8.20

Feedback
inhibition
The end product
acts as an inhibitor
of the first enzyme
in the series

Fig. 8.21

Cellular Respiration
and Fermentation

Chapter 9

Fig 9.2

Cellular respiration takes place in the cytosol and

mitochondria

Oxidative
phosphorylation
26-28 ATP

Glycolysis

Pyruvate
oxidation

Citric
Acid Cycle

C6H12O6 + 6O2 6CO2 + 6H2O + energy

Goal of cellular respiration: produce ATP

ADP phosphorylated in two ways
Oxidative phosphorylation
In the mitochondria!
associated with electrons falling toward oxygen
in the electron transport chain

Substrate-level phosphorylation
In the cytosol
An enzyme transfers PO4 directly to ADP

ATP in glycolysis is generated by substratelevel phosphorylation

An enzyme attaches Pi directly to ADP.
(The electron transport chain is not involved.)

Fig 9.7

How does the break down of

organic molecules release
energy?

Breaking down organic molecules

Some of energy released is stored as potential energy in

the ATP molecule
What happens to the rest of the energy?

Aerobic respiration: converting food to energy

Organic molecules (carbs, fats, and proteins) are
fuel for cells
Organic molecules + O2 CO2 + H2O + energy
Electrons in organic molecules are transferred to
oxygen.
Electrons release some of their potential energy when they
are transferred.
More H atoms provide more fuel
Why does oxygen take these electrons?

Fig 9.19

You have a friend who lost 7 kg (about 15

pounds) of fat on a regimen of strict diet and
exercise. How did the fat leave his body?
A) It was released as CO2 and H2O.
B) It was converted to heat and then released.
C)It was converted to ATP, which weighs
much less than fat.
D)It was converted to urine and eliminated
from the body.

Today: learn about catabolic reactions

through the breakdown of glucose
C6H12O6 + 6O2 6CO2 + 6H2O + energy
G = -686 kcal/mol

Energy is not released all at once! Instead is

released through a series of redox reactions
in which electron energy is transferred
between molecules.

Oxidation-Reduction (Redox) reactions

Gain of an electron = reduction.
Reduces the charge on the accepting molecule

Loss of an electron = oxidation.

Electrons stolen by more electronegative
molecule
Oxygen is especially electronegative; often
involved in oxidation reactions

Example: reaction between Na and Cl

Applied as a generalized example:

Example: oxidation of methane

Which of the reactants is oxidized and which is reduced?

Which is the oxidizing agent and which is the reducing agent?
Often an electron travels with a proton (H+)
Fig 9.3

Example: oxidation of glucose

Which of the reactants is oxidized and which is reduced?

Which is the oxidizing agent and which is the reducing agent?
Often an electron travels with a proton (H+)
When electrons are transferred, they lose potential energy and
free energy is released

The Electron transport helps to transfer

electrons from redox reactions to oxygen
ETC: series of molecules each with slightly
higher electronegativity than the last
Most ETC molecules are proteins

As electrons fall from one molecule to the

next, small amounts of energy released
At the end of the chain is oxygen most
electronegative
2 e- + 2 H+ + O2 H2O

Electron carriers can transfer energy from redox

reactions to the electron transport chain
Nicotinamide adenidinucleotide (NAD+) is a
coenzyme that can:
Accept an electron
Carry electrons to the
electron transport chain

Fig 9.4

Oxidized
Reduced

Oxidized

Reduced

NAD+ reaction summary

Fig 9.4

Dehydrogenase enzyme removes 2 H atoms (2 protons +

2 electrons) from organic fuel molecule.
NAD+ receives the 2 electrons but only 1 of the protons
The remaining proton is released into solution as H+

Electron transfer chain: step-wise release of energy

G = -53 kcal/mol

Fig 9.5

How is a molecule of glucose

converted to cellular energy?

Metabolic stages of cellular respiration

Fig 9.5

In glycolysis glucose is split into two 3carbon sugars

Glycolysis (sugar splitting)
These sugars oxidized to form
pyruvate

Takes place with or without O2

Also produces:
2 ATP molecules (by substratelevel phosphorylation)
2 NADH molecules (will be
used by the ETC)
Takes energy (2 ATP) to make
4 ATP

Glycolysis has two energy phases

Energy investment
2 ATPs consumed to
break glucose into two 3carbon molecules.

Energy payoff
4 ATPs and 2 NADH
generated as 3-carbon
molecules are oxidized
into pyruvate.

Net energy payoff

Fig 9.8

2 ATP are consumed

Fig 9.9

3-carbon molecules are oxidized to pyruvate

4 ATP are generated
2 NADH generated
Steps 6-10 occur twice for each glucose molecule

Fig 9.9

Output so far (per glucose molecule)

CO2
Glycolysis
Pyruvate
Acetyl CoA
Citric Acid Cycle
Oxidative
phosphorylation

TOTAL

FADH2

NADH

ATP
2

The free energy for the oxidation of glucose to CO2 and

water is -686 kcal/mol and the free energy for the
reduction of NAD+ to NADH is +53 kcal/mol. Why are
only two molecules of NADH formed during glycolysis
when it appears that as many as a dozen could be
formed?
A) Most of the free energy available from the oxidation
of glucose is used in the production of ATP in
glycolysis.
B) Glycolysis is a very inefficient reaction, with much of
the energy of glucose released as heat.
C) Most of the free energy available from the oxidation
of glucose remains in pyruvate, one of the products
of glycolysis.
D) There is no CO2 or water produced as products of
glycolysis.

Glycolysis releases only 25% of the energy

stored in glucose.
Remaining energy is stored in the two pyruvate
molecules.
Pyruvate enters the mitochondrion and is
converted to acetyl CoA
Acetyl CoA enters the citric acid cycle
Pyruvate breaks down to CO2, releasing more energy.

Pyruvate is oxidized before the Citric Acid Cycle

Pyruvate is oxidized before the Citric Acid Cycle

3 carbons

2 carbons

For each molecule of pyruvate, 1 CO2 is released and 1 NADH formed

Remember that there are 2 molecules of pyruvate for each
molecule of glucose
Fig 9.10

Output so far (per glucose molecule)

CO2
Glycolysis
Pyruvate
Acetyl CoA
Citric Acid Cycle
Oxidative
phosphorylation

TOTAL

0
1x2=2

FADH2

NADH

0
0

2
1x2=2

ATP
2
0

The Citric Acid (Krebs) Cycle reduces electron

carriers, produces ATP, and releases CO2

1. Acetyl CoA enters the cycle

2. Combines with 4-C
oxaloacetate to form 6-C
citrate molecule.
3. Citrate is broken down in 7
more steps.

2 CO2 molecules released.

3 NADH formed.
1 FADH2 (similar to NADH)
formed.
1 ATP formed (by substrate
phosphorylation).

4. Cycle ends with 4-C

oxaloacetate

joins with another acetyl CoA

to begin cycle again
Fig 9.11

Each step of the

CAC is catalyzed
by a specific
enzyme

Fig 9.12

Output so far (per glucose molecule)

CO2
Glycolysis
Pyruvate
Acetyl CoA

0
1x2=2

Krebs Cycle

2x2=4

Oxidative
phosphorylation

TOTAL

FADH2

NADH

0
2
0 1x2=2
1x2=2

3x2=6

ATP
2
0
1x2=2

Oxidative phosphorylation uses energy from

electrons to form ATP

Complete Model 1 questions

Electron transport chain

Collection of molecules (mostly enzymes)
embedded in inner mitochondrial membrane.
Infolding provide surface area for thousands of copies of
chain

ETC enzymes are built into the inner mitochondrial

membrane!

Fig 9.15

 Each protein
has a higher
electronegativity
than the one
before it
Does NADH or
FADH2 deliver
electrons
higher on the
chain?

Fig 9.13

Oxidative Phosphorylation uses energy from

falling electrons used to pump H+ into
intermembrane space
ATP synthase is the only protein
channel permeable to H+
As H+ diffuses back into
mitochondrial matrix through
ATP synthase, the enzyme
phosphorylates ADP
Chemiosmosis: using energy
from a proton gradient
https://www.youtube.com/
watch?v=PjdPTY1wHdQ

Fig 9.14

Energy output per glucose molecule

CO2

FADH2

NADH

ATP

Glycolysis
Pyruvate
Acetyl CoA

0
1x2=2

0
0

2
1x2=2

2
0

Krebs Cycle

2x2=4

1x2=2

3x2=6

1x2=2

Oxidative
phosphorylation

26-28

TOTAL

10

30-32

ATP yield depends on which electron carrier

is used (1.5 ATP/NADH, 2.5 ATP/FADH2)

Fig 9.16