CHAPTER 3

ENERGY, CATALYSIS, AND BIOSYNTHESIS

2004 Garland Science Puli!"in#
Ca$al%!i! and $"e &!e '( Ener#% % Cell!
3-1 If you weigh yourself on a scale one morning then eat four pounds of food during the day,
will you weigh four pounds more the next morning? Why or why not? Hint: What
happens to the atoms contained in the food and the energy stored in the chemical bonds
of food molecules?
3-2 Living organisms require a continual supply of energy to exist because they
a! defy the laws of thermodynamics"
b! convert it into heat energy, which powers biosynthetic reactions"
c! create order out of disorder inside their cells"
d! cause the entropy in the universe to decrease"
e! are closed systems isolated from the rest of the universe"
3-3 Life is thermodynamically possible because living things
a! release heat to the environment"
b! increase the degree of order in the universe"
c! reproduce themselves"
d! carry out energetically favorable reactions only"
e! can carry out a chain of reactions that is energetically unfavorable"
3-4 #he energy required by a human cell to grow and reproduce is provided by
a! the generation of order inside it"
b! its anabolic metabolism"
c! its catabolic metabolism"
d! generation of heat"
e! its biosynthetic reactions"
3-5 Which of the following statements about photosynthesis are #$%&?
a! 'hotosynthesis is irrelevant to the existence of animals"
b! 'hotosynthesis converts light energy into heat energy and chemical bond energy"
c! 'hotosynthesis consumes activated carrier molecules"
d! 'hotosynthesis is the opposite of carbon fixation in the &arth(s carbon cycle"
e! 'hotosynthesis increases global warming"
2)
3-6 )" *omplete the equation for respiration:
+ugars , --------- --------- , H
.
/ , heat energy , --------- energy
0" What does this process have in common with a fire that burns the polysaccharides
in wood? How does it differ?
3-7 1or each of the pairs )23 in 1igure 4567, pic8 the more reduced member of the pair"
1igure 4567
3-8 )re the following statements #$%& or 1)L+&? &xplain"
)" If oxidation occurs in a reaction, it must be accompanied by a reduction"
0" #he hydrogenation of an unsaturated fatty acid to a saturated fatty acid, as in the
conversion of vegetable oil to margarine, is an example of an oxidation reaction"
*" #he oxidation state of an atom influences its diameter"
30
3-9 1or each of the following sentences, fill in the blan8s with the best word or phrase
selected from the list below" 9ot all words or phrases will be used: each word or phrase
should be used only once"
0y definition, catalysis allows a reaction to occur more
------------------" *hemical reactions occur only when there is a
loss of ------------------ energy" &n;ymes act more
------------------ than other catalysts" ) catalyst reduces the
------------------ energy of a reaction"
activation free slowly
chemical bond 8inetic unfavorable
completely rapidly
favorable selectively
3-10 Which of the following reactions are energetically favorable?
a! base , sugar , phosphate nucleotide
b! amino acid , amino acid peptide
c! */
.
, H
.
/ sugar
d! sucrose */
.
, H
.
/
e! 9
.
, H
.

ammonia
3-11 Which of the following statements about en;ymes is correct?
a! *atalysis of an energetically unfavorable reaction by an en;yme will enable that
reaction to occur"
b! )n en;yme can direct a molecule along a particular reaction pathway"
c! )n en;yme can cataly;e many chemically different reactions"
d! )n en;yme can bind to many structurally unrelated substrates"
e! &n;ymes are permanently altered after cataly;ing a reaction"
3-12 Which of the following *)99/# be a reason that cells use en;ymes rather than heat to
increase the rate of biochemical reactions?
a! #he temperature increase required to speed up a reaction by an appreciable extent
is often huge"
b! $eactions cannot be coupled without en;ymes"
c! )n en;yme cataly;es <ust one or a very small number of different reactions: heat
would affect all the reactions in a cell"
d! &n;ymes change the equilibrium of biochemical reactions"
e! &n;ymes can accelerate reactions to a much greater extent than can heat"
3*
3-13 #he graph 456=5 is an energy diagram for an energetically favorable reaction of substrate
+ converted to product '" Indicate the following on the graph"
)" #he activation energy for the reaction
0" #he free energy change for the reaction
*" 3raw a new curve on the graph to indicate how an en;yme that converts + to '
will change the energetics of the reaction"
1igure 456=5
3-14 &nergetically favorable reactions are those that
a! decrease the entropy of a system"
b! increase the free energy of a system"
c! have a positive G"
d! decrease the free energy of a system"
e! create order in a system"
3-15 )" Which one or more of the following reactions will 9/# occur spontaneously
under the standard conditions that specify G?
a! )3' , '
i
)#' G > ,7"5 8cal?mole
b! glucose6=6phosphate glucose6@6phosphate G > 2="7 8cal?mole
c! glucose , fructose sucrose G > ,A"A 8cal?mole
d! glucose */
.
, H
.
/ G > 2@B@ 8cal?mole
0" Which of the reactions in ) could be coupled to any of the energetically
unfavorable reactions to enable them to occur?
32
3-16 &nergy diagrams for the conversion of a substrate + into a product ' are shown in 1igure
456=@" #he top diagram shows the original energy profile for the reaction" 1or each
description of an altered reaction below, choose a matching altered energy diagram,
labeled =6@, from the figure"
1igure 456=@
)" G is more positive
0" G is more negative
*" $eaction is cataly;ed
33
3" 9o change in G and no change in activation energy"
34
3-17 )ny reaction ) 0 is at equilibrium when
a! G > C"
b! G > C"
c! D)E > D0E"
d! G > G"
e! both forward and bac8ward rates reach ;ero"
3-18 *onsider the reaction F G in a cell at 57H*" )t equilibrium, the concentrations of F
and G are AC I and A I, respectively" %sing the equations below and your new
8nowledge, answer the following questions"
GH > 2C"@=@ ln K
eq
G > GH , C"@=@ ln DGE?DFE
$ecall that the natural log of a number z will have a negative value when z J =, positive
when z K =, and C when z > ="
)" What is the value of K
eq
for this reaction?
0" Is the standard free energy change of this reaction positive or negative? Is the
reaction F G an energetically favorable or unfavorable reaction under standard
conditions?
*" What is the value of the standard free energy? $efer to #able 56= in the textboo8
or use a calculator"
3" Imagine circumstances in which the concentration of F is =CCC I and G is
= I" Is conversion of F to G favorable? Will it happen quic8ly?
&" Imagine starting conditions in which the reaction F G is unfavorable, yet the
cell needs to produce more G" 3escribe two ways that this may be accomplished"
3-19 #he equilibrium constant for the binding of a protein to its ligand can depend on all of the
following &F*&'# the
a! number of noncovalent bonds formed between the protein and the ligand"
b! concentration of the ligand"
c! exact fit of the binding site to the ligand"
d! temperature"
e! pH"
3+
3-20 'rotein & can bind to two different proteins, + and I" #he binding reactions are described
by the following equations and values:
& , + &+ K
eq
for &+ > =C
& , I &I K
eq
for &I > .
0ased on the equilibrium constant values, which one of the following statements is
#$%&?
a! & binds I more tightly than +"
b! When + is present in excess, no I molecules will bind to &"
c! #he binding energy of the &+ interaction is greater than that of the &I interaction"
d! *hanging an amino acid on the binding surface of I from a basic amino acid to an
acidic one will li8ely ma8e the free energy of association with & more negative"
e! 0inding of + to & will decrease the entropy of these two proteins, and thus it is an
unfavorable reaction"
3-21 When the polymer F6F6F""" is bro8en down into monomers, it is Lphosphoryly;edM
rather than hydroly;ed, in the repeated reaction:
F6F6F""" , ' F6' , F6F""" reaction =!
Niven the G values of the reactions shown in #able 456.=, what is the expected ratio
of F6phosphate F6'! to free phosphate '! at equilibrium for reaction =?
a! =:=C
@
b! =:=C
O
c! =:=
d! =C
O
:=
e! =C
@
:=
#able 456.=
F6F6F""" , H
.
/ F , F6F""" G > 2O"A 8cal?mole
F , )#' F6' , )3' G > 2."B 8cal?mole
)#' , H
.
/ )3' , ' G > 27"5 8cal?mole
3,
3-22 #he following reactions ta8e place in a cell located next to a blood vessel"
F G G > 2=C 8cal?mole
G , /
.
P , */
.
G > ,C"A 8cal?mole
9ormally, the blood vessel brings in oxygen and ta8es away carbon dioxide, but years of
overindulgence have ta8en their toll, and it has become completely clogged with
cholesterol, cutting off the blood supply" Which of the following molecules would be
expected to accumulate in large amounts?
a! F
b! G
c! P
d! G and P
e! F and P
3-23 1igure 456.5 shows graphs of energy diagrams for the unfavorable reaction F G, the
favorable reaction G P, and the composite reaction F P"
)" 3raw lines near the composite reaction curve to indicate the free energy change
for each of the three reactions: GFG!, GGP!, and GFP!"
0" Is the composite reaction favorable or unfavorable?
1igure 456.5
3-
3-24 )" Gou are measuring the effect of temperature on the rate of an en;yme6cataly;ed
reaction" If you plot reaction rate against temperature, which of the graphs in
1igure 456.O would you expect your plot to resemble?
0" &xplain why temperature has this effect"
1igure 456.O
3-25 )re the following statements about diffusion #$%& or 1)L+&?
)" #he diffusion rate for small molecules is much slower in the dense gel of the
cytoplasm than in pure water"
0" #he diffusion rate is faster for large macromolecules than for small molecules"
*" #he rate of diffusion determines the association rate of all binding reactions"
3" #he number of reactions per second that an en;yme cataly;es is independent of
diffusion"
&" 3iffusion causes a molecule to move along a fairly straight path"
3-26 Which of the following features generally tend to increase the number of catalytic events
an en;yme accomplishes per second?
a! Increased substrate concentration
b! Iore positive free energy of binding between en;yme and substrate
c! 3ecreased strength of binding between en;yme and product
d! Increased diffusion rate of substrate
e! Increased salt concentration
3.
How We Know: Using Kinetics to Model and Manipulate Metabolic
Pathways
3-27 #he product G of an en;ymatic reaction absorbs light at the wavelength .@C nm and the
product P of another reaction absorbs at 5OC nm, unli8e the common substrate of the
reactions" ) spectrophotometer was used to measure the initial rate of production of G
and P by the reactions shown in 1igure 456.7)"
#he initial rates were measured for several independent reactions, all containing equal
amounts of en;yme ) or en;yme 0 and differing amounts of substrate F" ) graph was
made of the initial reaction rate v! plotted against the concentration of F DFE! 1igure
456.7!" Niven the data shown, are the following statements #$%& or 1)L+&?
1igure 456.7
)" V
max
)! J V
max
0!"
0" )t DFE > =C I, the amounts of en;ymes ) and 0 limit the rate of reaction"
*" K
I
)! K K
I
0!" Hint: D+E > K
I
when v > V
max
?."!
3" #he turnover number of en;yme ) is greater than the turnover number of en;yme
0" Hint: #urnover number > V
max
?Den;ymeE"!
&" If DFE > = I and both en;ymes are present, most of the substrate will be
converted to G rather than P"
3)
3-28 *onsider a description of an en;ymatic reaction pathway that begins with the binding of
substrate + to en;yme & and ends with the release of product ' from the en;yme"
& , + &+ &' & , '
%nder many circumstances,
K
I
> D&E D+E ? D&+E
)" What proportion of en;yme molecules are bound to substrate when D+E > K
I
?
0" $ecall that when D+E > K
I
, the reaction rate is V
max
?." 3oes your answer to 'art
) ma8e sense in light of this rate information?
Activated Carrier Molecules and Biosynthesis
3-29 Which of the following is 9/# a crucial benefit of using en;ymes to cataly;e biological
reactions?
a! &n;ymes are highly selective in which reactions they cataly;e"
b! &n;ymes can drive an unfavorable reaction by coupling it to a favorable reaction,
either directly or via activated carrier molecules"
c! &n;ymes ma8e reactions occur faster than without catalysis"
d! &n;ymes change the equilibrium of a reaction to ma8e it more favorable"
e! #he activity of en;ymes can be modulated by inhibitors and other small molecules
to respond to the needs of the cell at each moment"
3-30 *onsider an analogy between reaction coupling and money" In a simple economy, barter
provides a means of direct exchange of material goods" 1or example, the owner of a cow
may have excess mil8 and need eggs, whereas a chic8en owner has excess eggs and
needs mil8" 'rovided these two people are in close proximity and can communicate, they
may exchange or barter eggs for mil8" 0ut in a more complex economy, money serves as
a mediator for the exchanges of goods or services" 1or instance, the cow owner with
excess mil8 may not need other goods until three months from now or may want goods
from someone who does not need mil8" In this case, the LenergyM from providing mil8 to
the economy can be temporarily LstoredM as money, which is a form of LenergyM used for
many transactions in the economy" %sing barter and money as analogies, describe two
mechanisms that can serve to drive an unfavorable chemical reaction in the cell"
3-31 ) common means of providing energy to an energetically unfavorable reaction in a cell is
by
a! generation of a higher temperature by the cell"
b! transfer of a phosphate group from the substrate to )3'"
c! en;yme catalysis of the reaction"
d! coupling of )#' hydrolysis to the reaction"
e! coupling of the synthesis of )#' to the reaction"
40
3-32 )n anhydride formed between a carboxylic acid and a phosphate 1igure 4565.)! is
formed as a high6energy intermediate in some reactions in which )#' is used as the
energy source" )rsenate mimics phosphate and can also be incorporated into a similar
high6energy intermediate 1igure 4565.0!" #he reaction profiles for the hydrolysis of
these two high6energy intermediates are given in 1igure 4565.*" What is the effect of
substituting arsenate for phosphate in this reaction?
1igure 4565.
a! It forms a high6energy intermediate of lower energy"
b! It forms a high6energy intermediate of the same energy"
c! It decreases the stability of the high6energy intermediate"
d! It increases the stability of the high6energy intermediate"
e! It has no effect on the stability of the high6energy intermediate"
4*
3-33 Gou are studying a biochemical pathway that requires )#' as an energy source" #o your
dismay, the reactions soon stop, partly because the )#' is rapidly used up and partly
because an excess of )3' builds up and inhibits the en;ymes involved" Gou are about to
give up when the following table from a biochemistry textboo8 catches your eye"
Hydrolysis reaction G
creatine , )#'

en;yme ) creatine phosphate , )3' , 5 8cal?mole
)#' , H
.
/

en;yme 0
)3' , phosphate 27"5 8cal?mole
pyrophosphate , H
.
/

en;yme 3
. phosphate 27 8cal?mole
glucose @6phosphate , H
.
/
en;yme &
glucose , phosphate 25"5 8cal?mole
Which of the following reagents are most li8ely to revitali;e your reaction?
a! ) vast excess of )#'
b! Nlucose @6phosphate and en;yme &
c! *reatine phosphate and en;yme )
d! 'yrophosphate
e! 'yrophosphate and en;yme 3
3-34 Which of the following statements is #$%&?
a! #he oxidation of food molecules generates 9)3
,
"
b! 9)3H and 9)3'H are found in mutually exclusive parts of the cell"
c! #he ratio of 9)3'H:9)3'
,
is higher than the ratio of 9)3H:9)3
,
because
each molecule of 9)3'H is a stronger reducing agent than a molecule of 9)3H"
d! Iany en;ymes can use 9)3'H and 9)3H interchangeably"
e! /ne molecule of 9)3'H can cause the transfer of two hydrogen atoms"
3-35 Iatch the activated carrier molecules in List = with the groups they transfer, selected
from List ." Write the appropriate number beside each item in List ="
List 1 List 2
)" )#' =" 2*//
2
0" )cetyl *o) ." e
2
and H
,
*" 9)3'H 5" Nlucose
3" *arboxylated biotin O" 2'/
O
52
&" S6adenosylmethionine A" 2*H
5
@" 9ucleotide
7" 2*/*H
5
B" )mino acid
42
3-36 Which of the following processes must be coupled to an energetically favorable reaction
in order to occur?
a! *onversion of protein into amino acids
b! 'olymeri;ation of amino acids into polypeptides
c! *onversion of glucose to carbon dioxide and water
d! 1ormation of a bilayer from phospholipids in water
e! #he hydrolysis of )#'
3-37 #he en;ymes that cataly;e the synthesis of macromolecules do not also cataly;e their
brea8down by hydrolysis because
a! en;ymes can cataly;e reactions in only one direction"
b! hydrolysis is not an energetically favorable reaction"
c! the hydrolytic reaction is not the reverse of the reaction pathway that is used for
biosynthesis"
d! en;ymes are destroyed immediately after synthesis is completed"
e! biosynthesis proceeds more rapidly than hydrolysis"
3-38 #he energy required for the addition of a * nucleotide subunit *I'! to a growing
polynucleotide chain is originally derived from the hydrolysis of )#'" &xplain how this is
achieved"
43
An!/er!
3-1 9o, you will not weigh four pounds more the next morning because only a small portion
of the mass of the food will form components of the body" Iuch of the mass of food is
released as */
.
that is breathed out into the atmosphere or is released into the
environment as waste products" Iost of the energy contained in the chemical bonds of
the food molecules is converted to energy to maintain order among molecules in the
body, energy to move and thin8, and energy for anabolic or biosynthetic reactions to
rearrange the atoms from food into useful chemical structures biological small molecules
and macromolecules!" )s part of the process, a great deal of the bond energy is also
converted to heat"
3-2 *hoice c! is the answer" *hoice a! is incorrect as no system, living or otherwise, can
defy the laws of thermodynamics" *hoice b! is incorrect as living organisms do not use
heat to power biochemical reactions" Heat is produced in the course of biochemical
reactions" *hoice d! is incorrect: although living organisms are causing a local decrease
in entropy, they cannot cause a decrease in the entropy of the universe as a whole as that
would be a thermodynamic impossibility" *hoice e! is incorrect as living organisms are
not closed systems"
3-3 a! 0y releasing heat to their environment, living things increase the entropy of the
environment, thus compensating for the decrease in entropy inside cells" Living
things, therefore, satisfy the second law of thermodynamics" #hey use special
pathways for all their reactions that allow them to be energetically favorable"
3-4 *hoice c! is the answer" *atabolic reactions are the reactions in which a cell brea8s
down food molecules, releasing the energy held within their chemical bonds" *hoices
a!, b!, and e! are energy6requiring processes"
3-5 *hoice b! is true" 'hotosynthesis harvests light energy from the sun and converts it into
chemical bond energy" *hoice a! is false because food molecules and oxygen produced
by photosynthesis are the sole source of the energy that powers nearly all living non6
photosynthetic organisms" 'hotosynthesis activates carrier molecules as intermediates in
the LfixationM of inorganic carbon dioxide into organic sugar molecules so choices c!
and d! are false!" 0y consuming carbon dioxide and producing oxygen photosynthesis
lessens global warming cause by the greenhouse effect choice e! is false!"
3-6 )" +ugars , /
.
*/
.
, H
.
/ , heat energy , chemical bond energy
0" 0oth respiration and burning are reactions that use oxygen gas to oxidi;e complex
organic carbon molecules into */
.
, H
.
/" 0urning is an uncontrolled oxidation
in which the energy is all dissipated as heat: respiration is a multi6step, controlled
oxidation that harnesses the energy in high6energy chemical bonds that are useful
for anabolic reactions of cells"
44
3-7 )Qii: 0Qii: *Qi: 3Qii" LIore reducedM means having more electrons: gain of
electrons can result in an increased negative charge or a decreased positive charge and
can be due to an increase in the number of hydrogen atoms in a molecule"
3-8 )" #rue" ) redox reaction involves the complete or partial transfer of electrons from
one molecule or atom to another" #he donor is oxidi;ed and the recipient is
reduced in the reaction"
0" 1alse" Hydrogenation is a special 8ind of reduction reaction, involving receipt of
an electron from a donor molecule and acquisition of a proton, usually from
water" Hydrogenation increases the number of *6H bonds in a molecule"
*" #rue" #he diameter of an atom is influenced by the amount of negative charge, or
electron density, surrounding it" #he more reduced an atom becomes, the larger
will be its electron cloud"
3-9 0y definition, catalysis allows a reaction to occur more rapidly" *hemical reactions
occur only when there is a loss of free energy" &n;ymes act more selectively than other
catalysts" ) catalyst reduces the activation energy of a reaction"
3-10 d!
3-11 b!
3-12 d! &n;ymes change only the activation energy of a reaction, not the free energy
difference between reactants and products and thus cannot change the equilibrium
concentrations of reactants and products"
4+
3-13 +ee 1igure )56=5"
1igure )56=5
)" )ctivation energy is a minus b!"
0" *hange in free energy for the reaction is b minus c!"
*" )n en;yme will ma8e the value of a! smaller and leave the values for b! and c!
unchanged"
3-14 d!
3-15 )" a! and c!" /nly reactions with a negative G can occur spontaneously"
0" *oupling of reaction d! to either of the reactions a! or c! would provide an
overall negative G for the coupled reactions, thus enabling them to occur"
3-16 )Q.: 0Q5: *Q=: 3QO" Nraph O is the same as the graph for the original reaction in
terms of the relative energetic differences between substrates, transition states, and
products: the reaction diagram curve is simply positioned higher on the y6axis"
3-17 *hoice a! is correct" #he value of G for the reaction ) 0 is ;ero when there is no net
tendency for either ) 0 or 0 ), which is the definition of equilibrium" G is a
constant and is thus always the same regardless of whether the reaction has reached
equilibrium or not" #hus choices b! and d! are incorrect" *hoice c! is an incorrect
answer: although a particular reaction might be at equilibrium when the concentration of
substrate equals that of product, this is not true for most reactions" *hoice e! is not a
definition of equilibrium, but of a reaction that is not occurring at all"
4,
3-18 )" K
eq
> DGE?DFE > A I?AC I > C"="
0" #he standard free energy change, GH, is positive because K
eq
is less than ="
%nder standard conditions equal concentrations of F and G!, the reaction F G
is unfavorable"
*" GH > 2C"@=@ ln K
eq
> 2C"@=@ ln C"= > 2C"@=@! 2."5! > ="O 8cal?mol"
3" Ges, the conversion is favorable because the value of DGE?DFE is less than the
equilibrium value" However, the speed of the reaction cannot be determined from
the free energy difference" 1or example, combustion of this piece of paper is a
highly favorable reaction, yet it will not happen in our lifetime without a catalyst"
&" #he cell may directly couple the unfavorable reaction to a second, energetically
favorable reaction whose negative G has a value larger than the positive G of
the F G reaction: the coupled reaction will have a G equal to the sum of the
component reactions" )lternatively, more F will be converted to G if the
concentration of G drops: this may happen if G is converted to P in a second
reaction or if G is exported from the cell or compartment where the F G
reaction occurs"
3-19 b! #he equilibrium constant measures the strength of the interaction between a
protein and its ligand and is independent of the concentration of either the protein
or the ligand" #he strength of the protein6ligand interaction increases as the
number of noncovalent bonds between the two increases" #he shape of the
binding site affects the ability of the protein side chains to interact with portions
of the substrate molecule" 0oth temperature and pH can disrupt noncovalent
bonds that not only affect the binding, but are also responsible for 8eeping the
protein folded and thus functional"
3-20 *hoice c! is true" #he binding energy is the standard free energy of the binding reaction,
and thus is proportional to ln Req" )s the binding energy increases, the equilibrium
constant for the association reaction becomes larger" *hoices a! and b! are false,
because although & binds + more tightly than it does I, some & molecules will still be
bound to I molecules in most circumstances: indeed, if the number of I molecules far
exceeds the number of + molecules, more & molecules will be present in an &I complex
than in an &+ complex" *hoice d! is false: although not enough information is given to
be certain, it is li8ely that binding is normally strengthened by an ionic interaction
between a basic amino acid in I and an acidic amino acid in &Qthus, if anything, the
binding energy will be reduced by the amino acid change and the free energy change will
be less not more! negative" *hoice e! is false, because although the association of two
molecules often does decrease their own entropy, it can increase the entropy of other
molecules in the system" 1or example, heat release by the binding reaction can increase
the entropy of the system and its surroundings"
4-
3-21 c! $eaction = can be written as the sum of the three reactions given, since the )#'
used in +tep . is restored in +tep 5"
F6F6F""" , H./ F , F6F""" G > 2O"A 8cal?mole
F , )#' F6' , )3' G > 2."B 8cal?mole
)3' , ' )#' , H./ G > ,7"5 8cal?mole
+ince G values are additive, G
total
> C, and if G > C, Keq > =, meaning that
DproductsE?DreactantsE > =, and the ratio of F6' to ' is =:="
3-22 b! #he constant removal of */. and replenishment of /. by the blood normally
drives the reaction G P" #herefore, when */. is allowed to accumulate and /.
drops, G will accumulate" 0ecause the G of the first reaction is very negative,
G can accumulate to a very high level without causing significant amounts of F to
build up"
3-23 )" +ee 1igure )56.5 for correct labeling of figure"
1igure )56.5
0" 1avorable
3-24 )" Nraph =
0" 0y increasing thermal motion, increasing the temperature increases the rate of
diffusion of components and the number of collisions of sufficient energy to
overcome the activation energy" )n increase in temperature will thus increase the
reaction rate initially" However, en;ymes are proteins and are held together by
noncovalent interactions, so at very high temperatures, the en;yme will begin to
denature and the reaction rate will fall"
4.
3-25 )" 1alse" #he diffusion rate is almost as fast in the cytoplasm and in water"
0" 1alse" #he diffusion coefficient of a molecule decreases with increasing mass
shape is also a factor!"
*" 1alse" )lthough some binding reactions are diffusion6limited, others require an
unusually energetic collision to overcome an energy barrier"
3" 1alse" #he diffusion rate influences how often an en;yme will encounter and
thus bind! its substrate"
&" 1alse" 3iffusing molecules move in a Lrandom wal8,M in which they change
direction frequently after colliding with other molecules"
3-26 *hoices a!, c!, and d! are correct" #he higher the concentration and diffusion rate of
substrate, the more frequently a free en;yme will collide with and bind its substrate" #he
less tightly an en;yme binds its product, in general, the faster the product will dissociate
from the en;yme, leaving it free to bind a fresh substrate" *hoice b! is incorrect because
a more positive free energy of binding indicates it is less energetically favorable and thus
occurs less often" *hoice e! is li8ely to be false because many en;yme6substrate binding
interactions rely on ionic bonds that are wea8ened by high salt concentrations: in
addition, high salt concentrations can distort protein conformations"
3-27 )" #rue
0" #rue
*" 1alse
3" 1alse
&" #rue
3-28 )" When D+E is substituted for KI in the equation, it becomes clear that D&E > D&+E"
#hus, half of the en;yme molecules are free and half are bound to the substrate"
0" Ges" If half of the en;yme molecules are bound to the substrate, it ma8es intuitive
sense that the reaction rate is half of the maximum possible rate or half of the rate
observed when all of the en;yme molecules are bound to the substrate"
3-29 d! &n;ymes cannot change the equilibrium of a reaction"
3-30 0arter is analogous to the direct coupling of a favorable to an unfavorable reaction by a
single en;yme" Ioney is analogous to the storage of energy from a favorable reaction in
the form of high6energy bonds in an activated carrier molecule" +uch activated carrier
molecules can drive a huge variety of other unfavorable reactions in the cell, either by
being hydroly;ed to provide the needed energy for a reaction or by transferring the
activated chemical group to another molecule"
3-31 d!
4)
3-32 *hoice c! is correct" #he activation energy of the arsenate compound is extremely low,
as can be seen from the reaction profile, meaning that its high6energy intermediate is very
unstable and will be spontaneously hydroly;ed more rapidly than the phosphate
compound" In fact, this hydrolysis occurs rapidly without en;yme catalysis, even in
cellular conditions" #hus choices d! and e! are false" *hoices a! and b! are false as
more energy is released by the hydrolysis of the arsenoanhydride bond as inferred by the
greater difference in energy level between reactants and products in 1igure 4565.! so, by
definition, the arsenoanhydride bond is said to have more energy than the
phosphoanhydride bond"
3-33 c! )n excess of )#' will initially restore the reactions, but as )#' is hydroly;ed,
)3' will build up and inhibit the en;ymes again" 'yrophosphate does not loo8
li8e )#' and is therefore unli8ely to be used by the en;ymes as an alternative
energy source" 'yrophosphate , en;yme 3 will <ust heat things up" What you
need is a high6energy source of phosphate that can convert )3' bac8 to )#'"
+ince the G of the reaction,
)#' , creatine )3' , creatine phosphate,
cataly;ed by en;yme ) is greater than ;ero, the addition of creatine phosphate and
en;yme ) can be used to form )#' from )3', regenerating the )#' while also
forming creatine as a waste product"
3-34 *hoice e! is correct" 9)3'H has two electrons and one proton more than 9)3'
,
li8e
9)3H compared to 9)3
,
! and donates both electrons" 'rotons are always present in
solution" +o the recipient molecule effectively acquires two hydrogen atoms" *hoice a!
is false because oxidation of food molecules produces 9)3H, not 9)3
,
" *hioce b! is
false because 9)3H and 9)3'H can be found in the same parts of the cell, but are used
for different functions: this is possible because the en;ymes that recogni;e one do not
recogni;e the other: thus choice d! is also false" *hoice c! is false because the parts of
9)3'H and 9)3H that participate in reduction are identical, and thus they both have
essentially the same reducing power"
3-35 )QO phosphate group!: 0Q7 acetyl group!: *Q.: 3Q= carboxyl group!: &QA
methyl group!"
3-36 b! 'olymeri;ation of amino acids into polypeptides lead to the formation of peptide
bonds that have higher energy than the free amino acids and also represents an
increase in order" Hence, it can only be brought about via an input of energy" #he
other processes are thermodynamically spontaneous"
+0
3-37 c! Hydrolysis is not the reverse of the reactions cataly;ed by biosynthetic en;ymes"
1or instance, the reactions involved in $9) biosynthesis are:
polynucleotide
n!
, 9#' polynucleotide

n , =
!
, ''
i
''
i
, H
.
/ . '
i
"
#he reverse reactions are:
. '
i
''
i
, H
.
/
''
i
, polynucleotide
n , =!
polynucleotide
n!
, 9#',
9ot:
polynucleotide
n , =!
, H
.
/ polynucleotide
n!
, 9I' nucleoside
monophosphate!,
which is the reaction by which $9) is hydroly;ed" a! and b! are untrue:
en;ymes cataly;e both forward and reverse reactions, and hydrolysis is an
energetically favorable reaction" d! is untrue, since en;ymes are unchanged by
participating in catalysis" Whether e! is true or not for any particular reaction is
irrelevant"
3-38 In order to add the * nucleotide to the polynucleotide chain, it must be in the form of a
*#' cytidine triphosphate!" *onversion of *I' to *#' occurs by the sequential transfer
of two terminal phosphate groups from two molecules of )#'" #hus, hydroylysis of )#'
is coupled to phosphorylation of *I' and then to phosphorylation of *3'" +ubsequently,
the reaction that adds *I' to the polynucleotide chain releases pyrophosphate ''i!,
which is hydroly;ed to inorganic phosphate: this favorable reaction provides the energetic
drive for the overall condensation or polymeri;ation! reaction"
+*