ChapLer 6

ergy
W AblllLy Lo promoLe chage or do work
W forms
kleLlc assoclaLed wlLh movemeL
oLeLlal due Lo sLrucLure or locaLlo
W Chemlcal eergy eergy l molecular bods

Laws of Lhermodyamlcs
1 llrsL law
Law of coservaLlo of eergy
ergy caoL be creaLed or desLroyed
Ca be Lrasformed from oe Lype Lo aoLher
Secod law
1rasfer or LrasformaLlo of eergy from oe
form Lo aoLher lcreases eLropy or degree of
dlsorder of a sysLem

Laws of Lhermodyamlcs
1 llrsL law
?ou caL geL someLhlg for oLhlg
Secod law
?ou caL break eve
6
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HighIy
ordered

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Increase
More d|sordered
|n entropy
HighIy
ordered
Higher energy)
ower energy)

Chage l free eergy deLermles dlrecLlo

W 1oLal eergy usable eergy + uusable eergy
W ergy LrasformaLlos lvolve a chage l eLropy
W Lropy a measure of Lhe dlsorder LhaL caoL be
haressed Lo do work

C + 1S
W eLhalpy or LoLal eergy
W C free eergy or amouL of eergy for
work
W S eLropy or uusable eergy
W 1 absoluLe LemperaLure l kelvl (k)
10
SpoLaeous reacLlos
W Cccur wlLhouL lpuL of addlLloal eergy
W noL ecessarlly fasL
W key facLor ls Lhe free eergy chage
11
AC A 1 A S
W ergolc
AC 0 or egaLlve free eergy chage
SpoLaeous
8eleases eergy
W dergolc
AC 0 or poslLlve free eergy chage
8equlres addlLlo of eergy
noL spoLaeous

W ydrolysls of A1
W AC kcal/mole
W 8eacLlo favors
formaLlo of producLs
W ergy llberaLed ca
drlve a varleLy of
cellular processes
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Adenine (A)
Ribose
Phosphate groups
Phosphate (P
i
) Adenosine diphosphate (ADP)
Adenosine triphosphate (ATP)
+ ~
H H
OH
O
OH
H H
O O
O
H
2
C
O
-
NH
2
N
N
H
N
N
P OH
O
O
-
P O
-
O
O
-
P HO
~ ~
H H
OH
O
OH
H H
O O
O
H
2
C
O
-
NH
2
N
N
H
N
N
P O
O
O
-
P
O
O
-
P O
-
H
2
O
HydroIysis
of ATP
1
Cells use A1 hydrolysls
W A edergolc (eergyrequlrlg) reacLlo ca
be coupled Lo a eergolc (eergyreleaslg)
reacLlo
W dergolc reacLlo wlll be spoLaeous lf eL
free eergy chage for Lhe comblaLlo of
processes ls egaLlve
ATP
ADP P
Exergonic
(downhill)
reaction
Endergonic
(uphill)
reaction
Reactants
Products
Overall reaction
is downhill
Reactants ATP
Products ADP P
AG
1
AG
2
AG
12
Coupling oI Metabolic Reactions
This reaction will
not proceed because
it has a positive Iree
energy change
(AG).
Hydrolysis oI a
phosphate bond
has a negative
AG.
The coupled reaction
has a negative AG.
Coupling oI unIavorable (uphill)
reactions with ATP hydrolysis (a
downhillreaction) allows the overall
reaction to proceed, because the overall AG
is negative.
AG
1
AG
2
AG
12
II this number is
negative, the reaction
can proceed.
16
ymes ad 8lboymes
W A spoLaeous reacLlo ls oL ecessarlly a
fasL reacLlo
W CaLalysL a ageL LhaL speeds up Lhe raLe of a
chemlcal reacLlo wlLhouL belg cosumed
durlg Lhe reacLlo
W ymes proLel caLalysLs l llvlg cells
W 8lboymes 8nA molecules wlLh caLalyLlc
properLles
1
AcLlvaLlo eergy
W llLlal lpuL of eergy Lo sLarL reacLlo
W Allows molecules Lo geL close eough Lo cause
bod rearragemeL
W Ca ow achleve LraslLlo sLaLe where bods
are sLreLched
1
Cvercomlg acLlvaLlo eergy
W commo ways
eaL
uslg eymes Lo lower acLlvaLlo eergy
1
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Progress of an exergonic reaction
F
r
e
e

e
n
e
r
g
y

(
G
)
Transition state
Reactants
Reactant moIecuIes
Enzyme
ATP
GIucose
Products
Activation energy (E
A
)
without enzyme
Activation energy (E
A
)
with enzyme
Change
in free
energy
(G)
0
Lowerlg acLlvaLlo eergy
W SLrallg bods l reacLaLs Lo make lL easler
Lo achleve LraslLlo sLaLe
W oslLlolg reacLaLs LogeLher Lo faclllLaLe
bodlg
W Chaglg local evlromeL
ulrecL parLlclpaLlo Lhrough very Lemporary
bodlg
1
CLher eyme feaLures
W AcLlve slLe locaLlo where reacLlo Lakes
place
W SubsLraLe reacLaLs LhaL bld Lo acLlve slLe
W ymesubsLraLe comple ls formed whe
eyme ad subsLraLe bld

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GIucose
Substrates
Active site
ATP

Copyright The McGraw-Hill Companies, nc. Permission required for reproduction or display.
GIucose
Substrates
Active site
ATP
Enzyme-substrate compIex

GIucose
Substrates
Active site
ATP
Enzyme-substrate compIex
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Copyright The McGraw-Hill Companies, nc. Permission required for reproduction or display.
GIucose
Substrates
Active site
ATP
Enzyme-substrate compIex
GIucose-
phosphate
ADP
6
SubsLraLe bldlg
W ymes have a hlgh affllLy or hlgh degree of
speclflclLy for a subsLraLe
W Llke a lock ad key for subsLraLe ad eyme
bldlg
W lduced flL lLeracLlo also lvolves
coformaLloal chages
yme reacLlos
W SaLuraLlo plaLeau where esseLlally all acLlve slLes
are occupled by subsLraLe
I
f
veloclLy of reacLlo ear malmal raLe
W

subsLraLe coceLraLlo aL whlch veloclLy ls half

malmal value
Also called Mlchaells cosLaL
lgh

eyme eeds hlgher subsLraLe coceLraLlo

lversely relaLed Lo affllLy beLwee eyme ad subsLraLe

'
e
I
o
c
i
t
y
(
p
r
o
d
u
c
t
/
s
e
c
o
n
d
)
[Substrate]
A
B
'
max
2
'
max
C
D
A
60 sec
Low
B
60 sec
Moderate
C
60 sec
High
D
60 sec
(a) Reaction veIocity in the absence of inhibitors
0
Amount of
enzyme
Tube
Incubation
time
Substrate
concentration
'ery
high
1 m3 1 m3 1 m3 1 m3
K
M
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lhlblLlo
W CompeLlLlve lhlblLlo
Molecule blds Lo acLlve slLe
lhlblLs ablllLy of subsLraLe Lo bld
AppareL

lcreases more subsLraLe eeded

W nocompeLlLlve
Lowers I
f
wlLhouL affecLlg

lhlblLor blds Lo allosLerlc slLe oL acLlve slLe

0
K
M
with inhibitor [Substrate]
(b) Competitive inhibition
'
e
I
o
c
i
t
y
(
p
r
o
d
u
c
t
/
s
e
c
o
n
d
)
PIus competitive inhibitor
Substrate
Inhibitor
Enzyme
'
max
K
M
[Substrate]
(c) Noncompetitive inhibition
'
e
I
o
c
i
t
y
(
p
r
o
d
u
c
t
/
s
e
c
o
n
d
)
Substrate
Inhibitor
Enzyme
AIIosteric site
0
0
K
M
'
max
'
max
with inhibitor
PIus noncompetitive
inhibitor
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1
CLher requlremeLs for eymes
W rosLheLlc groups small molecules
permaeLly aLLached Lo Lhe eyme
W CofacLor usually lorgalc lo LhaL
Lemporarlly blds Lo eyme
W Coeyme orgalc molecule LhaL parLlclpaLes
l reacLlo buL lefL uchaged afLerward

ymes are affecLed by evlromeL

W MosL eymes fucLlo malmally l a arrow
rage of LemperaLure ad p
W CuLslde of Lhls arrow rage eyme fucLlo
decreases

0
0
10 20
R
a
t
e

o
f

a
c
h
e
m
i
c
a
I

r
e
a
c
t
i
o
n
30 40 50 60
High
Temperature (C)
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ulscovery of 8lboymes
uLll Lhe 10s scleLlsLs LhoughL all blologlcal caLalysLs were proLels
ulscoverles l Lwo labs chaged LhaL Lhlklg
1 8lbouclease (8ase ) foud l all llvlg orgalsms ls lvolved l
processlg L8nA molecules Work l Sldey AlLmas lab showed LhaL
Lhe 8nA subulL of 8ase aloe was able Lo cleave Lhe L8nA subsLraLe
Work l 1om Cechs lab showed LhaL a lLro l Lhe r8nA of Lhe clllaLe
@ff ls a selfspllclg lLro 1he 8nA caLalyes lLs ow spllclg
AlLma ad Cech shared Lhe 1 nobel rle l chemlsLry for Lhese
dlscoverles
numerous 8nA eymes or rlboymeshave bee dlscovered slce LhaL
Llme ledlg supporL Lo Lhe hypoLhesls LhaL 8nA preceded unA ad
proLel l Lhe early evoluLlo of llfe o earLh 1hls ls referred Lo as Lhe
8nA WorldhypoLhesls

Cvervlew of meLabollsm
W Chemlcal reacLlos occur l meLabollc
paLhways
W ach sLep ls coordlaLed by a speclflc eyme
W CaLabollc paLhways
8reakdow reacLlos are eergolc
W Aabollc paLhways
SyLhesls reacLlos are edergolc
MusL be coupled Lo eergolc reacLlo
Catabolic (energy-releasing) Metabolism
Higher energy starting materials
(e.g., sugars, lipids, etc.)
Lower energy products (e.g., CO
2
, H
2
O)
Metabolic energy (ATP,
reducing power)
Metabolic energy (ATP,
reducing power)
Anabolic (energy-requiring) Metabolism
Higher energy biological molecules
Lower energy starting materials

CaLabollc reacLlos
W 8reakdow of reacLaLs
W used for recycllg
W used Lo obLal eergy for edergolc
reacLlos
ergy sLored l eergy lLermedlaLes
W A1 nAu

ways Lo make A1
1 SubsLraLelevel phosphorylaLlo
yme dlrecLly Lrasfers phosphaLe from oe
molecule Lo aoLher molecule
Chemlosmosls
ergy sLored l a elecLrochemlcal gradleL ls
used Lo make A1 from Au ad
l
Synthesis
HydroIysis
ADP + P
i
ATP + H
2
O
Energy reIease
(Exergonic)
Energy input
(Endergonic)
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Synthesis and hydrolysis of ATP
1
8edo
W CldaLlo
8emoval of elecLros
W 8educLlo
AddlLlo of elecLros
W 8edo reacLlo
lecLro removed from oe molecule ls added Lo
aoLher

+ 8 A + 8

W A
as bee oldled
lecLro removed
W 8
as bee reduced
lecLro added
AII Energy MetaboIism Works This Way:
High energy eIectron donor
Low energy eIectron acceptor
At certain key steps, some energy is
stored, in the form of ATP and reducing
power ADH), for biological work.
biosynthesis, transport, maintenance,
etc.)

ergy lLermedlaLes
W lecLros removed by oldaLlo are used Lo
creaLe eergy lLermedlaLes llke nAu
W nAu
+
nlcoLlamlde adele dlucleoLlde
W nAu
Cldled Lo make A1
Ca doaLe elecLros durlg syLhesls reacLlos

Adenine
Nicotinamide
Nicotinamide
adenine
dinucIeotide
(NAD
+
)
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+ 2e
-
+ H
+
+
AD acts as the major high-energy electron carrier of the cell.

Reduction
Oxidation
Adenine
Nicotinamide
NADH
(an eIectron
carrier)
Nicotinamide
adenine
dinucIeotide
(NAD
+
)
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+ 2e
-
+ H
+
+

Aabollc reacLlos
W 8losyLheLlc reacLlos
W Make large macromolecules or smaller
molecules oL avallable from food
Metabolic energy (ATP,
reducing power)
Anabolic (energy-requiring) Metabolism
Higher energy biological molecules
Lower energy starting materials

8egulaLlo of meLabollc paLhways

1 Cee regulaLlo
1ur o or off gees
Cellular regulaLlo
Cellslgallg paLhways llke hormoes
8lochemlcal regulaLlo
leedback lhlblLlo producL of paLhway lhlblLs
early sLeps Lo preveL overaccumulaLlo of
producL
0
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Enzyme 1
InitiaI substrate
AIIosteric site
Active site
Feedback Inhibition

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Enzyme 1
InitiaI substrate
ConformationaI
change
AIIosteric site
Intermediate 1 Intermediate 2 FinaI product
Enzyme 2
Enzyme 3
Active site
FinaI product
Feedback Inhibition