Ground Rules of

Metabolism

Chapter 6
 Free Radicals

 Unbound molecular fragments with

the wrong number of electrons
 Highly reactive
 Can disrupt structure of molecules
 Superoxide

How many valence electrons are present?

What’s the charge on this anion?
Keeping Free Radicals
in Check

superoxide dismutase catalase

Figure 6.1
Page 96
This image illustrates the electrostatic field (yellow)
around an active site (red) of the enzyme
superoxide dismutase, which controls oxygen toxicity
by converting the superoxide radical to less
dangerous forms.
 Superoxide Dismutase
 Catalyzes the formation of
hydrogen peroxide from oxygen-
free radicals and hydrogen ions

 Accumulation of hydrogen
peroxide can be lethal to cells
 Catalase

Catalyzes the formation of oxygen

and water from hydrogen peroxide

2H2O2 ----------> 2H2O + O2

 Roundworm Experiments
 Diet supplemented with
superoxide dismutase and
catalase increased life span
of normal worms
 Diet also allowed worms
genetically engineered for
susceptibility to free
radicals to live normal life
span
What Is Energy?
 Capacity to do work

 Forms of energy
 Potential energy
 Kinetic energy
 Chemical energy
 What Can Cells Do
with Energy?
 Energy inputs become coupled
to energy-requiring processes
 Cells use energy for:
 Chemical work
 Mechanical work
 Electrochemical work
 First Law of
Thermodynamics
 The total amount of energy in the
universe remains constant

 Energy can undergo conversions

from one form to another, but it
cannot be created or destroyed
 One-Way Flow of Energy
 The sun is life’s primary energy
source

 Producers trap energy from the sun

and convert it into chemical bond
energy

 All organisms use the energy stored

in the bonds of organic compounds
to do work
 Second Law of
Thermodynamics
 No energy conversion is ever 100
percent efficient
 The total amount of energy is
flowing from high-energy forms to
forms lower in energy
 Entropy
 Measure of degree of disorder in a
system

 The world of life can resist the flow

toward maximum entropy only
because it is resupplied with energy
from the sun
 Energy Changes &
Cellular Work

Energy changes in cells tend to

run spontaneously in the direction
that results in a decrease in usable
energy
 Endergonic Reaction

glucose - a product with

more energy

+ 602 and 6H2O

Energy in
energy-poor 6 12
starting substances

Figure 6.5a,b
Page 100
 Exergonic Reaction

glucose -
energy-rich starting
substance

+
602

Energy out

6 6
products with less energy

Figure 6.5a,b
Page 100
 Structure of ATP
nucleotide base (adenine)

three phosphate groups

sugar (ribose)

Figure 6.6b
Page 101
 ATP: Main Energy Carrier

 ATP couples energy inputs and

outputs
 ATP/ADP cycle regenerates ATP
ATP

energy
energy
output
input
ADP + Pi
 Electron Transfers

 Oxidation - lose electron

 Reduction - gain electron
 Central to the formation of ATP
during photosynthesis and aerobic
respiration
 Participants in
Metabolic Pathways

Reactants  Energy

Intermediates Carriers

Products  Enzymes

 Cofactors
 Degradative and Anabolic
Pathways

large energy-rich
molecules

ADP
+ Pi BIOSYNTHETIC
DEGRADATIVE PATHWAYS
PATHWAYS (ANABOLIC)
(CATABOLIC)
ATP
simple organic
energy-poor compounds
products
ENERGY INPUT
 Types of Reaction
Sequences
A B C D E
F

LINEAR PATHWAY CYCLIC

PATHWAY
K J I G

BRANCHING PATHWAY

N M L H

Figure 6.8
Page 102
 Which Way Will
a Reaction Run?
 Nearly all chemical reactions are
reversible
 Direction reaction runs depends
upon
 Energy content of participants
 Reactant-to-product ratio
Chemical Equilibrium
RELATIVE RELATIVE
CONCENTRATION CONCENTRATION
OF REACTANT OF PRODUCT

HIGHLY
SPONTANEOUS

EQUILIBRIUM

HIGHLY
SPONTANEOUS

Figure 6.9
Page 103
 Chemical Equilibrium

 Energy in the reactants equals that

in the products
 Product and reactant molecules
usually differ in energy content
 Therefore, at equilibrium, the
amount of reactant almost never
equals the amount of product
 No Vanishing Atoms

 Law of conservation of mass

 Reactions rearrange atoms, but they
never destroy them
 As many atoms of each element in all
the products as there were in all the
reactants
 Electron Transfer Chains

 Arrangement of enzymes,
coenzymes, at cell membrane
 As one molecule is oxidized, next is
reduced
 Create H+ concentration and electric
gradients that are used for making
ATP
Enzyme Structure and
Function

Enzymes are catalytic molecules

They speed the rate at which

reactions approach equilibrium
 Four Features of Enzymes
1) Enzymes do not make anything
happen that could not happen on its
own. They just make it happen
much faster.

2) Reactions do not alter or use up

enzyme molecules.
Four Features of Enzymes

3) The same enzyme usually works

for both the forward and reverse
reactions.

4) Each type of enzyme recognizes

and binds to only certain
substrates.
 Activation Energy
 For a reaction
to occur, an
energy barrier starting
activation energy
without enzyme

must be substance activation energy

with enzyme

surmounted
 Enzymes make energy
released

the energy
by the
reaction

barrier smaller
products
Figure 6.12a
Page 105
 Activation Energy

Used to:
 Align reactive chemical groups
 Briefly destabilize electric charges
 Rearrange, create, and break
bonds
 Transition State

 Point when a reaction can easily run

in either direction, to product or back
to a reactant
 Substrate is bound most tightly to an
enzyme in this state
 Mechanisms of Bringing
about Transition State
 Helping substrates get together
 Orienting substrates in positions
favoring reaction
 Shutting out water
 Inducing changes in enzyme shape
Factors Influencing
Enzyme Activity
Coenzymes and cofactors

Allosteric regulators

Temperature

pH

Salt concentration
Allosteric Activation
allosteric enzyme active site
activator

vacant
allosteric active site cannot
binding bind substrate
site

active site
altered,
can bind
substrate
Figure 6.15a
Page 108
Allosteric Inhibition
allosteric inhibitor

allosteric
binding
site vacant;
active site
can bind
substrate

active site altered,

can’t bind substrate
Figure 6.15b
Page 108
 Feedback Inhibition
enzyme 2 enzyme 3 enzyme 4 enzyme 5

enzyme A cellular change, caused by a

1 specific activity, shuts down the
activity that brought it about

END
SUBSTRATE PRODUCT
(tryptophan)

Figure 6.16
Page 108
 Effect of Temperature
 Small increase in
temperature
increases
molecular
collisions,
reaction rates
 High
temperatures
disrupt bonds
and destroy the Figure 6.17b
Page 109
Effect of pH

Figure 6.17c
Page 109
 Beer, Enzymes, and
Your Liver
 Alcohol dehydrogenase
 Acetaldehyde dehydrogenase
 Cytochrome and catalase
 Heavy drinking destroys liver cells
and body’s ability to detoxify alcohol
 Alcohol Abuse
 Alcohol abuse generally leads to
three pathologically distinct liver
diseasesThese three conditions are:
 Fatty Liver
 Hepatitis
 Cirrhosis
 Fatty Liver

Normal Liver Fatty

Liver
Mitochondria malfunction
and fat accumulates
 Dietary Guidelines
Alcohol
 Dietary Guidelines for Americans If
you drink alcoholic beverages, do
so in moderation.
 What is Moderation?
Women: No more than one drink a day
Men: No more than two drinks a day
(This limit is based on differences
between the sexes in both weight and
metabolism.)
http://www.alcoholscreening.org/

 What’s a Drink?
 Count as a Drink ... •12 ounces of
regular beer (150 calories)•5 ounces
of wine (100 calories)•1.5 ounces of
80-proof distilled spirits (100
calories) (This limit is based on
differences between the sexes in
both weight and metabolism.)