Sección ii Bioenergética y el metaBoliSmo
de carBohidratoS y lípidoS
Bioenergética: la función
del ATP
Kathleen M. Botham, PhD, DSc y Peter A. Mayes, PhD, DSc
IMPORTANCIA BIOMÉDICA
La bioenergética, o termodinámica bioquímica, es el estudio de los
cambios de energía que acompañan a reacciones bioquímicas.
Los sistemas biológicos son en esencia isotérmicos y usan energía
química para impulsar procesos vivos. El modo en que un animal
obtiene combustible idóneo a partir de sus alimentos para propor-
cionar esta energía es básico para el entendimiento de la nutrición y
el metabolismo normales. La muerte por inanición ocurre cuando
se agotan las reservas de energía disponibles, y ciertas formas de
malnutrición se relacionan con desequilibrio de energía (maras-
mo). Las hormonas tiroideas controlan el índice de liberación de
energía (índice metabólico) y sobreviene enfermedad cuando fun-
cionan mal. El almacenamiento excesivo de energía excedente causa
obesidad, misma que es cada vez más común en la sociedad occi-
dental, padecimiento que predispone a muchas enfermedades,
como enfermedad cardiovascular y diabetes mellitus tipo 2, además
de que disminuye la esperanza de vida del individuo.
LA ENERGÍA LIBRE ES LA ENERGÍA ÚTIL
EN UN SISTEMA
El cambio de energía libre de Gibbs (ΔG) es la porción del cambio
de energía total en un sistema que está disponible para desempeñar
trabajo, es decir, la energía útil, también conocida como el potencial
químico.
Los sistemas biológicos se conforman
a las leyes generales de la termodinámica
La primera ley de la termodinámica establece que la energía total
de un sistema, incluso sus alrededores, permanece constante. Eso
92
11 Bender.indd 92
11
c A P í T u l o
implica que dentro del sistema total, la energía no se pierde ni se
gana durante cambio alguno; sin embargo, sí se puede transferir de
una porción del sistema a otra, o transformarse en otra forma
de energía. En sistemas vivos, la energía química se transforma ha-
cia calor o hacia energías eléctrica, radiante o mecánica.
La segunda ley de la termodinámica establece que para que un
proceso ocurra de manera espontánea, es necesario que la entro-
pía total de un sistema aumente. La entropía es la extensión de
trastorno o de aleatoriedad del sistema y alcanza su punto máximo
conforme alcanza el equilibrio. En condiciones de temperatura y
presión constantes, el vínculo entre el cambio de energía libre (ΔG)
de un sistema que está reaccionando y el cambio de entropía (ΔS) se
expresa por medio de la ecuación que sigue, que combina las dos
leyes de la termodinámica:
ΔG = ΔH - TΔS
donde ΔH es el cambio de la entalpía (calor) y T es la temperatura
absoluta.
En reacciones bioquímicas, dado que ΔH es aproximadamente
igual a ΔE, el cambio total de energía interna de la reacción, la rela-
ción anterior puede expresarse como sigue:
ΔG = ΔE - TΔS
Si ΔG es negativa, la reacción procede de modo espontáneo con
pérdida de la energía libre; esto es, es exergónica. Si, además,
ΔG es de gran magnitud, la reacción avanza casi hasta completarse
y es, en esencia, irreversible. Por otra parte, si ΔG es positiva, la
reacción sólo procede si es factible ganar energía libre; de modo
que es endergónica. Si, además, ΔG es de gran magnitud, el siste-
ma es estable, con poca o ninguna tendencia a que ocurra una re-
acción. Si ΔG es de cero, el sistema está en equilibrio y no tiene
lugar un cambio neto.
27/11/09 13:58:49
 capítulo 11 Bioenergética: la función del ATP 93

Cuando los reactivos están presentes en concentraciones de 1.0 reacciones exergónicas reciben el nombre de catabolismo (en gene-
mol/L, ΔG0 es el cambio de energía libre estándar. Para reacciones ral, la desintegración u oxidación de moléculas de combustible), en
bioquímicas, un estado estándar es definido como tener un pH de tanto que las reacciones sintéticas que acumulan sustancias se lla-
7.0. El cambio de energía libre estándar a tal estado estándar es indi- man anabolismo; los procesos catabólico y anabólico combinados
cado por ΔG0ʹ. constituyen el metabolismo.
El cambio de energía libre estándar puede calcularse a partir de Si la reacción que se muestra en la figura 11-1 va de izquierda a
la constante de equilibrio Keq. derecha, el proceso general debe acompañarse de pérdida de energía
libre como calor. Un mecanismo posible de acoplamiento podría
ΔG0ʹ = -RT ln K’eq imaginarse si un intermediario (I) obligatorio común tomó parte en
ambas reacciones, esto es,
donde R es la constante gaseosa y T es la temperatura absoluta (cap.
8). Es importante notar que la ΔG real puede ser mayor o menor que A+C→I→B+D
ΔG0ʹ, según las concentraciones de los diversos reactivos, incluso el
solvente, diversos iones y proteínas. Algunas reacciones exergónicas y endergónicas en sistemas
En un sistema bioquímico, una enzima sólo acelera el logro del biológicos están acopladas de este modo. Este tipo de sistema tiene
equilibrio; nunca altera las concentraciones finales de los reactivos un mecanismo integrado para el control biológico del índice de pro-
en equilibrio. cesos oxidativos, puesto que el intermediario obligatorio común
permite que el índice de utilización del producto de la vía sintética
(D) determine mediante acción de masa el índice al cual se oxida A.
LOS PROCESOS ENDERGÓNICOS En realidad, estos vínculos proporcionan una base para el concepto
PROCEDEN POR MEDIO DE de control respiratorio, el proceso que evita que un organismo se
consuma fuera de control. Las reacciones de deshidrogenación, que
ACOPLAMIENTO A PROCESOS están acopladas a hidrogenaciones por medio de un acarreador in-
EXERGÓNICOS termedio (fig. 11-2), proporcionan una extensión del concepto de
Los procesos vitales —p. ej., reacciones sintéticas, contracción mus- acoplamiento.
cular, conducción de impulsos nerviosos, transporte activo— obtie- Un método alternativo de acoplar un proceso exergónico a uno
endergónico es sintetizar un compuesto cHAPteRde alta
11 energía potencial
Bioenergetics: The Roleen
of ATP 93
nen energía mediante enlace químico, o acoplamiento, a reacciones
oxidativas. En su forma más simple, este tipo de acoplamiento pue- la reacción exergónica, e incorporar este nuevo compuesto hacia la
de representarse como lo muestra la figura 11-1. La conversión del reacción endergónica, lo que efectúa una transferencia de energía
chemical reactions, a standard
metabolito A en el metabolito B ocurre con liberación de energía state is defined as libre adesde
having pH la vía exergónicawhereas
molecules), hacia la endergónica
the synthetic (fig. 11-3). Lathat
reactions ven-build up sub-
of 7.0. The standard free-energy change
libre y está acoplada a otra reacción 0ʹen la cual se requiere energía li- at this taja
standard biológica
state de este
stances mecanismo
are termed es que el
anabolism. compuesto
The de
combinedenergíacatabolic and
is denoted by ΔG .
bre para convertir el metabolito C en el metabolito D. Los términos anabolic processes constitute metabolism.
exergónico y endergónico, The standard
en lugar free-energy
de los términos change can be
químicos calculated from
nor- If the reaction shown in Figure 11–1 is to go from left to
the equilibrium constant K .
males “exotérmico” y “endotérmico”, indicaneqque un proceso está AH right,
2 then Acarreador
the overall process must BH2 be accompanied by loss

acompañado de pérdida o ganancia, respectivamente, de energía li- of free energy as heat. One possible mechanism of coupling
ΔG0’ = -RT ln K’eq could be envisaged if a common obligatory intermediate (I)
bre en cualquier forma, no siempre como calor. En la práctica, un A Acarreador H2 B
proceso endergónico took part in both reactions, ie,
wherenoR puede existir
is the gas de manera
constant and Tindependiente,
is the absolute temperature
sino que debe ser(Chapter
un componente 8). It is important to exergónico-ender-
de un sistema note that the actual ΔG FIGURA
may be 11-2 Acoplamiento de reacciones A+C→I→B+D
de deshidrogenación e
gónico acoplado larger
donde or el cambio neto general es exergónico. Las
smaller than ΔG depending on the concentrations
0ʹ hidrogenación por medio de un acarreador intermedio.
of the various reactants, including the solvent, various ions, Some exergonic and endergonic reactions in biologic sys-
A and proteins. tems are coupled in this way. This type of system has a built-in
A
In a biochemical system, an enzyme only speeds up the mechanism for biologic control of the rate of oxidative pro-
attainment of equilibrium; it neverCalor alters the final concentra- cesses, since the common obligatory intermediate allows the
tions of the reactants at equilibrium. rate of utilization of the product of the synthetic path (D) to
Ex
er
gó

D determine by mass action the rate at which A is oxidized. In-

ni
ca

D
deed, these relationships supply a basis for the concept of re-
Energía libre

E
ENDERGONIC PROCESSES PROCEED BY spiratory control, the process that prevents an organism from
Energía libre

burning out of control. An extension of the coupling concept

COUPLING TO EXERGONIC PROCESSES is provided by dehydrogenation reactions, which are coupled
Energía
The vitalicaprocesses—eg, synthetic reactions, química muscular contrac- to hydrogenations by an intermediate carrier (Figure 11–2).
ón An alternative method E of coupling an exergonic to an en-
tion, de
r gnerve impulse conduction, active transport—obtain en-
n dergonic process is to synthesize a compound of high-energy
ergy
E by chemical linkage, or coupling, to oxidative reactions.
In its simplest form, this type of coupling may be represented potential in the exergonic reaction and to incorporate this
C as shown in Figure 11–1. The B conversion of metabolite A to new compoundB into the endergonic C
reaction, thus effecting a
metabolite B occurs with release of free energy and is coupled transference of free energy from the exergonic to the ender-
A+C B + D + Calor
to another reaction in which free energy is required FIGURA
to con- 11-3 gonic pathway (Figure
Transferencia de energía11–3). The biologic
libre desde una reacciónadvantage of this
FIGURA 11-1vert metabolitedeCuna
Acoplamiento to reacción
metabolite una exergonic
D. Thea terms
exergónica and haciamechanism
exergónica una endergónicais that the compound
mediante un compuesto of intermedio
high potential energy,
endergónica. endergonic, rather than the normal chemical terms de alta energía (~E,). unlike I in the previous system, need not be structurally
“exother-
mic” and “endothermic,” are used to indicate that a process
is accompanied by loss or gain, respectively, of free energy in AH2 Carrier BH2

any form, not necessarily as heat. In practice, an endergonic

process cannot exist independently, but must be a component A Carrier H2 B
of a coupled exergonic-endergonic system where the overall
11 Bender.indd 93
net change is exergonic. The exergonic reactions are termed FIGURE 11–2 Coupling of dehydrogenation and hydrogenation
27/11/09 13:58:53
 alters the muscular
final concentra- burning
cesses,
to out
hydrogenations
since
of control.
the common
An
by extension
an intermediate
obligatory
of the
intermediate
carrier
coupling
(Figure
concept
allows
11–2).
the
Creactions,
PROCESSES contrac-
is provided
rate of An
utilization
byalternative
dehydrogenation
of the
method
product
reactions,
of coupling
of thewhich
synthetic
an exergonic
are coupled
path to
(D)
antoen-
ctive transport—obtain en-
ling,
ns, muscular
to oxidativecontrac-reactions. to hydrogenations
determine
dergonicby process
mass
by anaction
isintermediate
to synthesize
the ratecarrier
ata compound
which (Figure
A is oxidized.
of
11–2).
high-energyIn-
oupling
ransport—obtain
may be represented
en- deed,
An potential
alternative
these relationships
in method
the exergonic ofsupply
coupling
reaction
a basis
an exergonic
and
for the to incorporate
concept
to an en- of re-this
oES
nversion PROCEED BY
oxidative of metabolite
reactions. A to spiratory
dergonic new process control,
compound is to synthesize
into
the process
the endergonic
a that
compound
prevents
reaction,
ofan high-energy
organism
thus effecting
from a
g
f free
may energy
be represented
and is coupled potential
burning in out
the of
transference exergonic
control.
of free energyAn
reaction
extension
fromandtheoftoexergonic
the
incorporate
coupling to theconcept
thisender-
NIC PROCESSES
onenergyof metabolite
is required A94 toto con-new iscompound
Sección provided
gonicii pathway by
into dehydrogenation
Bioenergética they elendergonic
(Figure 11–3).de reaction,
metabolismo reactions,
The biologic
carbohidratos thus
ywhich effecting
lípidos are coupled
advantage aof this
D.
actions,
energy The terms
and 94 contrac-
is exergonic
muscular coupled 94 Section
and ii mechanism
Section
to ii of
Bioenergetics
hydrogenations
transference free&isthe
Bioenergetics Metabolism
by
energy
that& thean
the of Carbohydrates
intermediate
from
compound
Metabolism of& Lipids
carrier
theof exergonic high
Carbohydrates &(Figure
to potential
Lipids 11–2).
the ender- energy,
ive
al
y is chemical
transport—obtain
requiredterms to con- potencial
“exother- alta, ~
en- gonic E An, al
pathway contrarioI in de
alternative
unlike (Figure method
11–3).
the I previous
en elThesistema previo,
of coupling
biologic
system, an
needno necesita
exergonic
advantage anCuadro
tothis
not beofstructurallyen- 11-1 Energía libre estándar de hidrólisis
ng,
d terms exergonic
totoindicate
oxidative that aestar
reactions.
and relacionado
process dergonic
mechanism de modo thatestructural
isprocess theis to con A, of
synthesize
compound B,a high
C o D,potential
compound lo queofper- energy,de algunos organofosfatos de importancia bioquímica
high-energy
mical
spectively,
pling terms
may be related
of“exother-
free mite
represented to que
energy A,in
related ~B,
EC,
to A, or
B, D,
sirva C,
,potential
unlike comoallowing
or
I inD,
un
in allowing
the
the AH 2 to serve
transductor
exergonic
previous
E E to as
deserve a transducer
energía
reaction
system,
Carrier as desde
need a and
transducer
notunatobe BHof
amplia2TABLE
ofincorporate
structurally TABLE 11–111–1
this Standard Free Energy
Standard of Hydrolysis
Free Energy of of
of Hydrolysis
energy from
energy a wide range of exergonic reactions to an equally ΔG0’
ndicate
ersion
In practice,
of
thatmetabolite
a an
process gama
endergonic
A tode from new a wide
reacciones range ofinto
endergónicas
compound exergonic
hacia unareactions
the endergonicgama igual to de
anamplia
reaction, equally
thusSome Organophosphates
Some
deeffecting a Organophosphates of Biochemical Importance
of Biochemical Importance
vely,
y,
reebut energy
ofmust
freeandbe wide
energy range
wide
in range
aiscomponent
coupled of endergonic
reacciones of endergonic
otransference
procesos reactions
AH free or
2 of reactions
endergónicos, processes,
energy or from
como
Carrier such
processes,
biosíntesis, as
suchbio- 2as bio-
contracción
the exergonic
BH to the ender- Compuesto kJ/mol kcal/mol
ΔG0’ ΔG0’
ic
nergy
actice,
systemisanrequired
where syntheses,
endergonicthemuscular,
to muscular
syntheses,
overall muscular
con- excitación
gonic contraction,
pathway contraction,
nerviosa
A
nervous
y transporte
(Figure nervous
11–3). excitation,
activo. En la and
The excitation,
Carrier H2
biologic célula and
B
viva, of this
advantage
active transport. InFIGURE
theInliving cell, the principal high-energy Fosfoenolpiruvato −61.9 −14.8
must
The
gonic terms areelactive
exergonic
bereactions
a component and transport.
principal
termed intermediario
mechanism the11–2
isliving
de cell,
altaCoupling
that the principal
energía
the compound
Carrier of H
of high-energy
odehydrogenation
compuesto high acarreador
potential energy,
and hydrogenation Compound
Compound kJ/molkJ/mol kcal/mol kcal/mol
em
down
chemical
whereor terms intermediate
oxidation
the overall (designado
“exother- or
intermediate
of fuel ~ E carrier
or
, en compound
carrier
unlike
reactions byI compound
A
la figuraan (designated
11-3),
in intermediate
the es(designated
previous ~
system, ~
trifosfato
elcarrier.
2
E in Figure
de in
need
E
B
Figure
adenosina
not be structurally Carbamoil fosfato −51.4 −12.3
Phosphoenolpyruvate
Phosphoenolpyruvate −61.9 −61.9 −14.8 −14.8
oreactions
indicateare that11–3)
termed is adenosine
11–3)
(atp).
a process is adenosinetriphosphate
triphosphate (AtP). (AtP).
FIGURE 11–2 Coupling of dehydrogenation and hydrogenation 1,3-bisfosfoglicerato −49.3 −11.8
Carbamoyl Carbamoylphosphate phosphate −51.4 −51.4 −12.3 −12.3
ectively,
or oxidation
of freeofenergy
fuel in reactions by an intermediate AH2 carrier.Carrier BH2 (a 3-fosfoglicerato)
n practice, an endergonic
HIGH-ENERGY
HIGH-ENERGY
LOS
but must be a component FOSFATOS PHOSPHATESPHOSPHATES PLAY PLAY A A
ADE ALTA ENERGÍA TIENEN (to 3-phosphoglycerate)
1,3-Bisphosphoglycerate
1,3-Bisphosphoglycerate
Creatina fosfato
(to 3-phosphoglycerate)
−49.3 −49.3 −43.1 −11.8 −11.8 −10.3

system whereCENTRAL
Heat CENTRAL ROLE ROLE IN FUNDAMENTAL
ENERGY
IN ENERGY CAPTURE CAPTURE
A Carrier H2 B
the UNA
overall FUNCIÓN EN LA Creatine
ATP → AMP + PPi
phosphate
Creatine phosphate −43.1 −43.1
−32.2
−10.3 −10.3
−7.7
onic reactions AND AND
are termed TRANSFER
CAPTACIÓN TRANSFER
FIGURE A
Y 11–2
LA TRANSFERENCIA
Coupling of dehydrogenation and hydrogenation ATP → ADP + Pi −30.5 −7.3
D ATP →ATP AMP →+AMP PPi + PPi −32.2 −32.2 −7.7 −7.7
own or oxidation
Heat
of fuel reactions by an intermediate carrier.
DE
In order toENERGÍA
In order maintain
to maintain livinglivingprocesses,
processes,all organisms
all organisms must must ob- ob- ATP →ATP Glucosa 1-fosfato −20.9 −5.0
D ADP→+ ADP Pi + Pi −30.5 −30.5 −7.3 −7.3
D tain supplies
tain supplies of freeof energy
free energy from from their their
environment.environment. Auto- Auto- PPi −19.2 −4.6
Atrophic
trophic finorganisms
de mantener
organisms procesos
utilize simple
utilize vivos, todos
exergonic
simple los
exergonic organismos
processes;
E
processes; eg,deben
theeg, obte-
the GlucoseGlucose 1-phosphate 1-phosphate −20.9 −20.9 −5.0 −5.0
Free energy

ner ofenergía libre(green

desde su ambiente. Los
theorganismos Feautotróficos
Fe→ Fe3+ PPi PPFructuosa
D 6-fosfato −15.9 −3.8
energy energy sunlight
of sunlight plants),
(green the reaction
plants), E Fe →
reaction 2+ 2+ 3+
−19.2 −19.2 −4.6 −4.6
(some utilizan
bacteria).
(some
Chemical procesos
bacteria).On theexergónicos
A
Onother simples;
hand,hand,
the other por ejemplo,
heterotrophic
heterotrophic la energía
organ-organ- de la i
Free energy

Heat Glucosa 6-fosfato −13.8 −3.3

isms luz solar (plantas freeverdes), labyreacción Fe2+metabolism
→ Fe3+metabolism
(algunas bacterias).
energy Fructose 6-phosphate
Fructose 6-phosphate −15.9 −15.9 −3.8 −3.8
obtain
isms free
obtain energy by coupling
energy their
coupling their to the to the Glicerol 3-fosfato −9.2 −2.2
D Chemical Por
breakdown otraof
breakdown parte, ofloscomplex
complex organismos
organic heterotróficos
molecules
organic molecules obtienen
in their E energía libreGlucose
environ-
in their environ- 6-phosphate
Glucose 6-phosphate −13.8 −13.8 −3.3 −3.3
ment.alment.
acoplar su
allmetabolismo aATP
la desintegración a de moléculas orgáni-
energy
abreviaturas: PPi, pirofosfato inórganico; Pi, ortofosfato inorgánico.
In all Inthese organisms,
these organisms, plays
ATP plays a central role
central inrole
thein the Glycerol 3-phosphate
Glycerol 3-phosphate −9.2 −9.2 −2.2 −2.2
cas
transference complejas en
of freeofenergy su ambiente.
from from En todos
the exergonic estos E organismos, el ATP D Nota: Todos los valores tomados de Jencks (1976), excepto los valores para el PPi, que
to the
transference free energy the exergonic E toender-the ender- son de Frey y Arabshahi (1995). Los valores difieren entre investigadores, según las
gonictiene una función fundamental enis laatransferencia de energía libre
B Abbreviations:
Abbreviations:PPi, pyrophosphate; Pi, inorganic
PPi, pyrophosphate; orthophosphate.
Pi, inorganic orthophosphate.
processes
gonic processes (Figure 11–3).11–3).
(Figure ATP ATP nucleoside
is aB nucleoside triphos- triphos-
Free energy

C condiciones precisas en las cuales se hicieron las mediciones.

phatedesde los procesos exergónicos hacia los endergónicos (fig.groups.
11-3).Note:
El AllNote:
Heat values Alltaken
valuesfromtakenJencks
from(1976),
Jencks except
(1976), that for that
except PPi which
for PPis from Frey
which andFrey and
is from
containing
phate containing adenine, ribose,ribose,
adenine, and three
and phosphate
three phosphate groups. Arabshahi (1995). Values
Arabshahi (1995).differ
Values between investigators,
differ between depending
investigators,
i
on the precise
depending on the precise
B
In ATP
its In es
reactions un nucleósido
in FIGURE
theincell, trifosfato
theit11–3functionsque contiene adenina, ribosa y tres
its reactions cell, it Transfer Bas of
functions the asMgthe complex
Mg complex
Chemical 2+ 2+ conditions
rgonic to an endergonic free energy Cfrom an exergonic tounder
an which
conditions underthe measurements
which were made.
the measurements were made.
energy
grupos
(Figure 11–4).
(Figure fosfato.
11–4). En sus reacciones
endergonic reaction viaena high-energy
la célula, funciona intermediate como el
compound (~E).
to an endergonic
complejo
The importance
The de
FIGURE Mg2+of
importance (fig.
11–3 11-4).
phosphates
of Transfer
phosphates in intermediary
of free inenergy
intermediary
fromE
metabo- metabo-to an de baja energía, ejemplificados por los fosfatos éster que se encuen-
an exergonic
lism became La
lism became importancia
evident
endergonic with
evident de los
the
with
reaction fosfatos
discovery en el metabolismo
of theof
thea high-energy
via discovery role
theofrole
intermediateATP,intermediario
ATP, ad-found
of ad-
compound (~E). in thein intermediates
found the intermediates of glycolysis,
of glycolysis, have have G0ʹ values
G0ʹ values
se hizo evidente con el descubrimiento de la función del ATP, difos- tran en los intermediarios de la glucólisis, tienen valores de G0ʹ me-
enosine diphosphate
enosine diphosphate (ADP), and inorganic
(ADP), and inorganic phosphate phosphate (Pi) in(Pi) insmaller than that
smaller than ofthat ATP, while while
of ATP, in high-energy
in high-energy phosphates
phosphates
B
fato de adenosina (ADP) y fosfato inorgánico (Pi) en la glucólisis nores que los del ATP, mientras que en los fosfatos de alta energía
glycolysis (Chapter
glycolysis 18).
(Chapter 18). the value
the is
value higheris than
higher that
than of ATP.
that of The
ATP. components
The components of thisof this
eat (cap. 18).
B C el valor es mayor que el del ATP. Los componentes de este último
latter latter
group,group, including ATP, ATP,
including are usually anhydrides
are usually anhydrides (eg, the (eg, the
grupo, incluso el ATP, por lo general son anhídridos (p. ej., el 1-fos-
onic to an endergonic FIGURE 11–3 Transfer of free energy from an exergonic 1-phosphate
to1-phosphate
an of 8:30:09
1,3-bisphosphoglycerate),
ofPM1,3-bisphosphoglycerate), enolphosphates
enolphosphates (eg, (eg,
The The Intermediate fato del 1,3-bisfosfoglicerato), enolfosfatos (p. ej., fosfoenolpiruva-
3/26/2009

endergonicValue
Intermediate Value
reaction for
via a thefor Free
high-energythe Free intermediate compound phosphoenolpyruvate),
phosphoenolpyruvate),
(~E). and phosphoguanidines
and phosphoguanidines (eg, creatine
(eg, creatine
El valor intermedio para la energía libre phosphate, to) y fosfoguanidinas (p. ej., creatina fosfato, arginina fosfato). La
Energy Energy of Hydrolysis
of Hydrolysis of ATP of ATP Has Has ImportantImportant 3/26/2009 phosphate, arginine
PM argininephosphate).
phosphate). The intermediate
The intermediate position of of
position
de hidrólisis del aTP tiene gran posición intermedia del ATP permite que desempeñe una función
8:30:09

Bioenergetic
Bioenergetic Significance
Significance ATP allows
ATP it
allowsto play
it to an important
play an importantrole in energy
role in transfer.
energy The
transfer. The
importante en la transferencia de energía. El cambio de energía libre
importancia bioenergética high free-energy
high free-energy change on hydrolysis
change on hydrolysis of ATP ofisATP
en el momento de la hidrólisis del ATP se debe a alivio de la repul-
dueistodue reliefto of
relief of
The standard
The standard free energy
free energy of hydrolysis
of hydrolysis of a numberof a number of bio- of bio-chargecharge repulsion of adjacent
repulsion of adjacentnegatively charged
negatively oxygen
charged atomsatoms
oxygen
Elchemically
chemically cuadro 11-1
important muestra
important phosphatesla energía
phosphates libre
is shown estándar
is shownin Table in de 11–1.
Table la hidrólisis
An Anand
11–1. de sión de carga de átomos de oxígeno adyacentes que tienen carga
diversos fosfatos importantes desde el punto de vista bioquímico. toandstabilization
to stabilization of theofreaction
the reaction products, especially
products, phos-phos-
especially
estimate of theof
estimate comparative
the comparative tendency of each
tendency ofof theof
each phosphate
the phosphatephate,phate, negativa, y a estabilización de los productos de la reacción, en es-
Un estimado de la tendencia comparativa de cada uno de los grupos as resonance as8:30:09
resonancehybrids. OtherOther
hybrids. “high-energy
“high-energy compounds”
compounds”
groups to transfer
groups to a suitable
to transfer acceptor
to a suitable may be
acceptor may obtained
be obtained from fromare thiol pecial fosfato, como híbridos de resonancia. Otros “compuestos de
3/26/2009 PM

fosfato para a are esters

thiol esters involving coenzyme
involving coenzyme A (eg,Aacetyl-CoA),
(eg, acetyl-CoA), acyl acyl
the ∆G the0ʹ
of 0ʹ
of transferir
∆Ghydrolysis 0ʹ
at
hydrolysis hacia
37°C.at un value
The
37°C. aceptor
The for
value idóneo
thefor puede
hydrolysis
the obtenerse
hydrolysisof of alta energía” son ésteres tiol que incluyen a la coenzima A (p. ej.,
carriercarrierprotein, aminoamino
protein, acid esters involved
acid esters in protein
involved synthe-
in protein synthe-
partir
the terminal de
the terminal la ΔG
phosphate de
phosphate la hidrólisis
of ATP ofdivides a 37°C.
ATP divides El
the listthevalor
into para
listtwo la hidrólisis
intogroups. del acetil-CoA), proteína acarreadora de acilo, y ésteres aminoácidos
two groups.sis, S-adenosylmethionine
fosfato terminal del ATP divide la lista en dos grupos. Los fosfatos sis, S-adenosylmethionine (active(activemethionine),
methionine),UDPGlc UDPGlc (uri- (uri-
Low-energy
Low-energy phosphates,phosphates, exemplified
exemplified by thebyester the phosphates
ester phosphatesdine diphosphate comprendidos en la síntesis de proteína, S-adenosilmetionina (me-
dine diphosphate glucose), and PRPP
glucose), and PRPP (5-phosphoribosyl-1-
(5-phosphoribosyl-1-
tionina activa), UDPGlc (uridina difosfato glucosa) y PRPP (5-fos-
pyrophosphate).
pyrophosphate).
NH NH
forribosil-1-pirofosfato).
2 NH22
N N
N
N N
N
Mg2+ Mg
Mg2+
2+
N
High-Energy Phosphates
High-Energy
Los fosfatos Are Arese designan
Phosphates
de alta energía
N
Designated by ~
Designated
mediante ~P
by ~P
N N
N N

O– O–––
O
O O–––
O
O O–
O –

– ––
The symbol
The ~P indicates
symbol
El símbolo ~P indicates
indicathat the
que elgroup
that attached
the group
grupo to the
fijo alattached
enlace, entobond,
elthe bond, de
momento
O P O PPP O
O OO
O PPP O
O PP
O CHO
2OO CH
CH22 O
O
on transfer to an to
ontransferencia
transfer appropriate
an appropriate
hacia acceptor,
un aceptor resultsresults
acceptor,
apropiado, dainpor
transfer of la trans-
in transfer
resultado of
O O
OO O
O
O OO
C
H CHHC
C
H HH
CC the larger
the quantity
larger
ferencia of freeofenergy.
dequantity
la cantidad free
más grandeFor this
energy. deFor reason,
energía thePor
this reason,
libre. term
the
esteterm
motivo,
H
groupgroup
transfer
algunos potential,
transfer
prefierenpotential,
el término potencial
ratherrather
than de transferencia
“high-energy
than “high-energy bond,”bond, isde ”grupo,
is
H H
H HH
preferred
másbyque
preferred some.
by Thus,
some.
“enlace ATP
alta contains
deThus, two
ATP contains
energía”. high-energy
De estatwo elphos-
high-energy
manera, ATPphos-contiene
OH OH OH
OH OH OH
phate phate
groups
dos grupos and ADP
groups and contains
ADP
fosfato one,
contains
de alta whereas
energíaone, the contiene
y elwhereas
ADP phosphate
the phosphatein mientras
uno, in
FIGURE 11–411-4
FIGURE
FIGURA 11–4
Adenosine triphosphate
Adenosine
El trifosfato (ATP) shown
triphosphate
de adenosina (ATP) como elAMP AMP
as the as the
(ATP)shown
mostrado (adenosine
que el(adenosine monophosphate)
fosfato en elmonophosphate) is of the
AMP (monofosfato is oflow-energy
de the low-energy
adenosina) type,
es deltype,
tipo de
magnesium complex.
magnesium
complejo ADP forms
complex.
de magnesio. ADP aforms
El ADP similar complex
a similar
forma with similar
complex
un complejo Mgwith
2+
con2+.Mg2+. since since
. Mg itbaja
is a itenergía,
normal ester
is a normal
porque link
es (Figure
ester link
un 11–5).
(Figure
enlace éster11–5).
normal (fig. 11-5).

Murray_CH11_PTR.indd 94
Murray_CH11_PTR.indd 94 3/26/2009 8:30:09 PM
3/26/2009 8:30:09 PM
11 Bender.indd 94 27/11/09 13:59:00
 ermediate
D, allowingorEcarrier
drates & Lipids
to serve compound
as a transducer (designated of ~TABLE
E in Figure 11–1 Standard Free Energy of Hydrolysis of
Phosphoenolpyruvate −61.9 −14.8
range
–3) is of adenosine
exergonictriphosphate
reactions to an (AtP). equally Some Organophosphates of Biochemical Importance
gonic reactions or processes, such as bio- Carbamoyl phosphate −51.4 −12.3
ΔG0’
rtion contraction, nervous excitation, and
IGH-ENERGY
nsducer
the living cell, the
of
ii Bioenergetics TABLE PHOSPHATES
11–1
& the Metabolism
principal
of Carbohydrates
high-energy Standard PLAY
&Free
A Compound 1,3-Bisphosphoglycerate
Lipids Energy of Hydrolysis of
(to 3-phosphoglycerate) kJ/mol kcal/mol
−49.3 −11.8
an equally SomeIN Organophosphates of Biochemical Importance
ENTRAL
ier compound
uch as bio-
ROLE (designated ENERGY
~E in Figure CAPTURE Creatine phosphate−61.9 −43.1
cHAPteR 11 Bioenergetics: The Role of ATP
−10.3
95
Phosphoenolpyruvate −14.8
ND B, C,TRANSFER
riphosphate
ation, orand
(AtP).
D, allowing E to serve as a transducer of TABLE
ΔG 0’

11–1 Standard Free Energy of Hydrolysis of −7.7

capítulo 11 Bioenergética: la función del ATP 95
Carbamoyl phosphate ATP → AMP + PPi −51.4 −12.3 −32.2
igh-energy
tiona widetorange
ii of exergonic
Bioenergetics & the Metabolism reactionsall
of toorganisms
Carbohydrates an equally
& Lipids Some
–ob- –Organophosphates of Biochemical Importance
order maintain livingCompound
processes, kJ/mol
must
O–1,3-Bisphosphoglycerate
O– O
– kcal/mol
O– → ADP + Pi −49.3
Phosphoenolpyruvate
Fosfoenolpiruvato 1,3-Bisphosphoglycerate
1,3-Bisfosfoglicerato
E Y
of PHOSPHATES
in
endergonic
n supplies Figure reactions
of freePhosphoenolpyruvate
energy PLAY
or processes,
fromAdenosine A environment.
their such as bio- Auto-
(to−61.9
O O ATP
3-phosphoglycerate) −14.8 –
–
−11.8
ΔG
−30.5
0’
−7.3
muscular contraction, nervous excitation,
Adenosina and
Succinyl- Succinil-
LE IN ENERGY CAPTURE
O P O
O P O P O P O Oxidative
ophic organisms utilize simple exergonic processes; eg, the P O Glucose P O 1-phosphate CoA CoA −20.9 −5.0 Fosforilación
phosphorylation
oxidativa
port.
B,
ergy C, Inor the
D, allowing
living cell,
E to
Carbamoyl the serve
principal
phosphate
of sunlight (green plants), the reaction Fe → Fe as a transducer
high-energy O of Creatine−51.4 TABLE
Ophosphate 11–1
Compound −12.3 Standard−43.1 Free Energy
kJ/mol of
−10.3 Hydrolysis kcal/mol of
ER
2+ O 3+ O O
PPOi −19.2 −4.6 Creatine
eaor wide carrierrangecompound
ofOn exergonic
the (designated
reactionshand, ~ toEaninequally Figure Some + Organophosphates of Biochemical−7.7 Importance CreatinaP P
ome
Y A bacteria). other
1,3-Bisphosphoglycerate orheterotrophic
Adenosine ATP P −49.3
→organ-
AMP PP
PPhosphoenolpyruvate
P i −11.8 −32.2 −61.9 −14.8
P
ofnosineendergonic triphosphate (AtP).
free reactions orcoupling
processes, such oas bio-
Adenosina P P P
Fructose 6-phosphate −15.9 P −3.8
ms living
obtain processes, energy all(toorganisms
3-phosphoglycerate)
by must their ob-metabolism to the+ P
URE
muscular
eakdown
energy from contraction,
of complextheir nervous
environment.
Creatine organic
phosphate
excitation,
molecules
Adenosine
Auto- in their environ-and
Trifosfato
ATP → ADP
triphosphate
de
−43.1
Carbamoyl
adenosina(ATP)i (ATP) phosphate
Glucose
−10.3 6-phosphate
−30.5 −51.4
ΔG0’
−7.3
−13.8 −12.3 −3.3
Creatine
(Store of (Reserva P ) de
P )
port. In thethese
living cell, the principal high-energy Glucose
O– in1-phosphate – Compound −20.9 kJ/mol −5.0 kcal/mol
ATP ATP Creatina
ent.
tilize
NERGY In simple
all exergonic
organisms,
PHOSPHATES processes;ATP plays
eg,
PLAY the
a central
A role the
1,3-Bisphosphoglycerate
– O –
O Glycerol
−49.3 −11.8
or carrier O −7.7 3-phosphate −9.2 −2.2
ofcompound
ATP →(designated ~E Fe3+in Figure
AMP + PP −32.2 (to 3-phosphoglycerate)
nsference
green plants), free theenergy
reaction from Fe2+ thei
→ exergonic toPPthe ender-
AL ROLE ob- IN ENERGY CAPTURE Phosphoenolpyruvate −19.2 −61.9 −4.6 Ciclo −14.8
–
s must
nnosine triphosphate (AtP). Adenosine O
Adenosina O P O P
i O P O
−30.5 Creatine Abbreviations:
P O – ATP/ADP
PPi, pyrophosphate; Pi, inorganic orthophosphate. del
nic theprocesses
other hand,
(FigureATPheterotrophic
→ 11–3).
ADP +ATP Pi organ-
is a nucleoside triphos- phosphate −7.3 −43.1 cycleATP/ADP −10.3
ent.
ANSFER Auto- Fructose
O 6-phosphate
Carbamoyl
O Note:
phosphate
All values taken from −15.9 −51.4except
Jencks (1976), −3.8
that for −12.3
PPi which is from P Frey and
ate
rgycontaining
by coupling adenine,
their
Glucose metabolism
ribose,
1-phosphate and to
three the phosphate groups.
−20.9
O O
Arabshahi −5.0 (1995). Values differ between investigators, depending on the precise P Glucose 6-phosphate
Glucosa 6-fosfato
ses; eg, the ATP → AMP + PP −32.2ADP −3.3 −7.7
lex
its
NERGY reactions
organic molecules
in the cell, in it
3+PHOSPHATES PLAY A o Adenosina their
functions environ- asor the Mg
Adenosine Glucose
2+
complex
P 6-phosphate
1,3-Bisphosphoglycerate
P conditionsi under which the −13.8 measurements−49.3 wereADP made. −11.8 Other phosphorylations,
e → Fe living processes,
maintain
2+
PPi all organisms must ob- −19.2 ATP P
(to→
P
ADP +−4.6
3-phosphoglycerate)
Otras fosforilaciones,
gure
ganisms, 11–4). ATP plays a central role inAdenosine the Pi −30.5 −7.3 activations,
activaciones
sLofROLE
hic organ-
free energy IN ENERGY
from their environment. CAPTURE Auto-
Difosfato
Glycerol 3-phosphate
diphosphate
de adenosina (ADP)(ADP) −9.2 −2.2 Glucose 1,6- 1,6-
Glucosa and endergonic
y procesos
energy
The importance
from the exergonic of phosphates
Fructose to theinender-
6-phosphate intermediary metabo- −15.9Creatine phosphate
Glucose 1-phosphate −3.8 −43.1
−20.9 Glicerol 3-fosfato
Glycerol 3-phosphate −10.3
−5.0 bisphosphate processes
anisms
lism
ANSFER to utilize
the simple exergonic processes; eg, the
Abbreviations: – PPi,–pyrophosphate; found in Pi, inorganic
the orthophosphate.
intermediates of glycolysis, have G
bisfosfato
0ʹ
values
endergónicos
mure became
11–3).evident ATP is with
a nucleoside
the discovery triphos- of the2+ role of 3+ ATP,
O ad-O
unlight
r environ- (green plants), the reaction Fe → Fe
Glucose 6-phosphate Note: −13.8
All values ATP taken → AMP
from + −3.3
Jencks PP i than that of FIGURE
(1976), except that for PP −32.2
which 11–6
is from Frey
in high-energy and −7.7
phosphates
osine
nine, ribose, diphosphate and three (ADP), phosphateand inorganic groups. phosphate O (P
Arabshahi )PP
(1995). in–iValuesOsmaller
–
differ between investigators, depending
ATP,i −19.2 while
FIGURA
on the precise 11-6of−4.6
Role ATP/ADP
Función cycle
del in transfer
ciclo del ATP/ADPof high-energy
en la transferencia de
maintain
eria).
role inOn theliving
the other processes, hand,
Glycerol allheterotrophic
3-phosphateorganisms Adenosine
must organ- ob-
Adenosina P
−9.2
Oi OP
the value
−2.2 is higher thanphosphate.
that of ATP. The
fosfato de alta energía. components of this
he colysis
cell, it (Chapter
functions 18).as the Mg complex 2+ conditions under ATP → ADP
which
Fructose the + Pi
measurements
6-phosphate were made. −30.5
−15.9 −7.3
−3.8
sthe
free
of ender-
free
energy energyby coupling
from their their metabolism Auto-
environment. to the O O latter group, including ATP, are usually anhydrides (eg, the
Abbreviations: PPi, pyrophosphate; Pi, inorganic orthophosphate. Glucose
anisms
deof triphos-
complex utilizeorganic
simple molecules
exergonic processes; in their environ- eg, the Glucose1-phosphate
6-phosphate −20.9
−13.8 −5.0
−3.3
of phosphates Note: in intermediary
All values taken from metabo-
Jencks or Adenosine
(1976), except that for
o3+Adenosina P PP which
i P
1-phosphate
is from Frey and of 1,3-bisphosphoglycerate), maintained, but when enolphosphates
the ATP/ADP(eg, ratio is high, their con-
he
unlight
ate
these Intermediate
groups.organisms,
(green plants),
with the discovery
ATPValue
Arabshahi
of the
the
playsreaction
(1995). Values
rolewhich for
a central
of ATP, differthe
Fe role→
2+
between Free
ininvestigators,
Fe
ad- monophosphate
the independing
found PPthe
Glycerol
i intermediates
onphosphoenolpyruvate),
3-phosphate
the precise of glycolysis, and
centration have
phosphoguanidines
−19.2
−9.2 G
can
0ʹ
values
increase
−4.6
−2.2
to act(eg,as creatine
a store of high-energy phos-
ria).
2+
ofcomplex
free
Onenergy the other fromhand,
conditions heterotrophic
the exergonic
under the to the organ-
Adenosine
measurements ender- were made. (AMP)(AMP) fuente de energía para laposition of muscular, los fosfágenos per-
contracción
nergy(ADP),of andHydrolysis
inorganic phosphate of ATP (Pi)Has in Important
Monofosfato
smaller than de adenosina
Fructose that 6-phosphate
Abbreviations: phosphate,
ofPPATP, while
, pyrophosphate;arginineinP high-energy
phosphate).
phate
, inorganic −15.9
(Figure phosphates
The
orthophosphate.
miten que
intermediate
11–7).
sus
−3.8
concentraciones se mantengan, pero cuando la pro-
sses
free energy(Figure by 11–3).
coupling ATP
FIGURE their
is a11–5
FIGURA nucleoside
metabolism
11-5 triphos-
toofthe the
ATP,value is ADP
higher ATP than
i
allows
that of
it toATP.
i
playThe an important
components role ofacts
in
oenergetic
8). Significance Structure Estructura ADP,
del ATP,and
Note: AMP
All valuesshowing
y AMP, que
taken the
muestra
from Jencks la
(1976), except When
that for PP ATP which isthis
energy
from asFreya transfer.
phosphate
and Thedonor to form those
of
ning
y metabo-
complex
adenine, organic
ribose, molecules
and
position three
and the
posición yphosphate
in their environ-
elnumber
número ofgroups.
de latter group,
high-energy
fosfatos
Glucose
phosphates
deArabshahi
alta energía
6-phosphate
including high
(1995). (~P). free-energy
Values ATP, differare usually
betweenchange porción
−13.8
anhydrides
on hydrolysis
investigators, depending
i
ATP/ADP
(eg,of
on ATPthe
−3.3 es
is due
the precise alta, su
to relief concentración
of puede incrementarse
e
of
ons standard
these
ATP, inorganisms,
the free found
ad- cell, it ATP energy
functionsin of the
plays as intermediates
hydrolysis of
the Mgrolecomplex
a central 2+ a number of
in 1-phosphate
the glycolysis,
of bio-
conditions haveunder Gwhich
0ʹ
values
the measurements compounds
were para
made. of
actuar lowercomo freeuna energy
reserva of
de hydrolysis
fosfato de (Table
alta 11–1),
energía (fig. 11-7).
Glycerolof 1,3-bisphosphoglycerate),
charge repulsion of adjacent
3-phosphate
the enolphosphates
negatively
−9.2
phosphate group charged
(eg,is−2.2 oxygen atoms
invariably converted to one of low en-
emically important smaller than
phosphates that is of
shown ATP, inwhile
Table in11–1.high-energy
An phosphates Cuando el ATP actúa como un donador de fosfato para formar
ate
4).
hate
of free Value
(P i
in for
)energy from the theFree exergonic to the ender- phosphoenolpyruvate), and PPi,to and
stabilization
phosphoguanidines ofergy,
the orthophosphate.
reaction (eg, products,
creatine especially phos-
imate
portance
sses
rolysis of
(Figure the the
comparative
of phosphates
of11–3).
ATP HIGH-ENERGY
value
ATP in
Has
is higher
tendency
is intermediary than
of
a nucleoside triphos-
Important each PHOSPHATES
thatof
metabo- of
the ATP.
phosphate
phosphate,
Abbreviations:
The components
Note:arginine
All values
ACT
phate,phosphate).
taken
AS
pyrophosphate;
of this
as resonance
from JencksThe
Pi, inorganic
(1976), intermediate
hybrids.
eg,
los
except thatOther
compuestos
for PP position
“high-energy
which
de energía
of0ʹFrey and
is from
libre
compounds” más baja de hidrólisis (cuadro 11-1),
oups
eningevident to transfer
adenine, with ribose,latter
to aTHE group,
and “ENERGY
suitable
the discovery three including
acceptor
of the phosphate may ATP,
role ofCURRENCY” be
ATP, are
obtained
groups. usually
ad- allows found
from anhydrides
OF in the
THE (eg,
intermediates
CELLthe of glycolysis,
el grupo i have
fosfato G values
siempre se convierte en uno de baja energía, por
ignificance ATP it to
Arabshahi playare
(1995). an
thiol
Values important
esters
differ involving
between role in energy
investigators, coenzyme transfer.
depending Aon(eg,The acetyl-CoA), acyl
the precise
eons ∆G
hosphate 0ʹ
of hydrolysis
in the(ADP), 1-phosphate
cell, it and at
functions LOS
37°C.
inorganic of
TheFOSFATOS
as the1,3-bisphosphoglycerate),
value
phosphate for
Mg complex
2+ the
(Phighi
DE
hydrolysis ALTA smaller
) in free-energy change of
conditions ENERGÍA
enolphosphatesthan
under that
which
carrieron theof
(eg, ATP,
measurements
protein,
hydrolysis
while
amino were
of ATP
in high-energy
ejemplo,
made.
acid isestersdue to involved
phosphates
relief ofin protein synthe- KINASE GLYCEROL
energy
).terminal
Chapter of18). hydrolysis
phosphate ATPofof ACTÚAN
phosphoenolpyruvate),
isnumber
aATP able to act
divides oftheasCOMO
aand
bio- donor
list into ofLA
phosphoguanidines
two
charge “MONEDA
high-energy the value
groups.
repulsion of
is(eg,
phosphate higher creatine tothan
S-adenosylmethionine
sis,adjacent
formthat of ATP. The components of this
negatively charged (active
oxygen methionine),
atoms UDPGlc (uri-
portant
w-energy
t phosphates
portance is phosphate,
ofphosphates,shown
phosphates thosein
DEin arginine
compounds
exemplified
Table
intermediary
ENERGÍA” 11–1. phosphate).
by below
Anthemetabo-
ester
DE and
The
it inphosphates
Table
LA to
intermediate
latter
11–1.group,
CÉLULA
stabilization
Likewise,
dine
position
of
including
the
withofthe
diphosphate
reaction
ATP, are usually
products,
glucose),
Glycerolanhydrides
especially
and
+ Adenosine (eg,Pthe P
PRPP phos- (5-phosphoribosyl-1-
P GLICEROL
arative
evidenttendency with the ATPof allows
necessary
each
discovery of theitofenzymes,
to playroleanofADP
phosphate
the important
ATP,can ad- acceptrolefound1-phosphate
in high-energy
energy in the transfer.
ofintermediates
1,3-bisphosphoglycerate),
The
phosphate of glycolysis, enolphosphates
have G Glycerol 0ʹ
(eg, P + Adenosine CINASA
values
phate, as resonance pyrophosphate).
hybrids. Other “high-energy compounds”
rmediate Value for thepuede Free Glicerol + Adenosina P P
a suitable(ADP),
hosphate acceptor high
andto free-energy
may form
El beATP
inorganic ATP
obtained change
from
phosphate from on hydrolysis
those
actuar (Pcompounds
como ) in un of
smaller
phosphoenolpyruvate),
ATP
donadorabove isthan
due
ATP
de to
that
fosfatoinrelief
theof
de of
ATP,
table.
alta and while
energía in high-energy (eg,
phosphoguanidines creatine P P P
phosphates
ber of bio- NH i are thiol esters involving coenzyme A (eg, acetyl-CoA), acyl
of s atHydrolysis
37°C. The value chargeof
In for ATP
repulsion
effect, Has
the formar ofImportant
an AtP/ADP
hydrolysis adjacent of N cyclenegatively connects the
phosphate,
charged
value those oxygen
isdebajo
arginine
higher
processes atoms
delthanphosphate).
thatthatenofelATP. The The intermediate
components positionof this ofGlicerol
2

ehapter
11–1. 18). An para los compuestos carrier queprotein,
están poramino acid mismo
esters involved in protein synthe- P + Adenosina P P
ate
getic of ATP divides
Significance and to
generate
the stabilization
list into ~P two to of
those
Ngroups.
cuadro 11-1. De igual modo, the reaction
processes products,
that latter
ATP
utilize allows
group,
especially
~P
con las enzimas necesarias, it including
to
(Figure play
phos- an
11–6), ATP,
important are usually
role in anhydrides
energy transfer.
(eg, The
the
phosphate sis, S-adenosylmethionine High-Energy (active el ADP
Phosphates
methionine), UDPGlc Are (uri-
ates, exemplified phate,
by
Mg 2+ as resonance
continuously
thepuedeesteraceptar hybrids.
consuming
phosphates fosfato N deOther
and alta “high-energy
regenerating
energía 1-phosphate
high para free-energy
ATP.
formarcompounds”
of ATP
This 1,3-bisphosphoglycerate),
change
occurs
a partiron de
at hydrolysis
los of ATP enolphosphates
is due to relief (eg, of
ained
d freefrom
rmediate energyValue of
are hydrolysis
athiol for
very the
esters
rapid
compuestos
of involving
aFree
rate,
numbercoenzyme
N
since
que se hallanAn the
dine
total
diphosphate
of bio- Aphosphoenolpyruvate),
charge
ATP/ADP(eg, acetyl-CoA),
glucose),
Designated
repulsion
pool
por arriba del ATP en el cuadro. En efecto, is of
and
acyl
adjacent
extremely
PRPP
and by ATP
phosphoguanidines
negatively Allows
El aTP
(5-phosphoribosyl-1-
~P charged the
permite
oxygen
(eg, Coupling
creatine
atoms el of
acoplamiento de
ydrolysis
mportantofphosphates is shown O– in Table 11–1.pyrophosphate).
O–
Thermodynamically
reacciones desfavorablesofUnfavorable
the bond, en el aspecto
–
f Hydrolysis of ATP Has Important
O
carrier
small protein,
unand ciclo amino
sufficient
de atp/adp acid esters
to maintain conecta involved
an losphosphate,
and
active
procesos to
intissue
stabilization
protein
The
que arginine
forsymbol
generansynthe-
onlyof phosphate).
a~P theindicates
few reaction
con los Thethat
products,
intermediate
the group especiallyposition
attached phos- to
wo
he comparative
groups. –O sis, Ptendency
O 2 P Oof P
NH each O of the
2 Ophosphate
getic
phosphates
ansfer to Significance
a suitable
S-adenosylmethionine
seconds.procesos que
CH
(active
lo utilizanfrom methionine),
ATP
phate, allows
as UDPGlc
resonance
(fig. 11-6), lo que consume y regenera ATPon it to
transfer play (uri-
hybrids.
anto important
an OtherReactions
appropriate role termodinámico,
“high-energy
in energy
acceptor, to Favorable
transfer.
compounds”
results The
in a Ones
favorables
transfer of
O acceptor O N may beglucose),
Cobtained
dine diphosphate
There O
are three major C and PRPP
sources high
are
of (5-phosphoribosyl-1-
~P thiol
free-energy esters
taking
the involving
part
larger change in on
en-
quantity coenzyme
hydrolysis
of free A of (eg,
ATP
energy. acetyl-CoA),
is
For due thisto relief
reason, acyl
of the term
Thede manera continua. H Esto sobreviene a un índice muy rápido, dado
N
d
hydrolysis
free energy at 37°C.
ofpyrophosphate).
hydrolysis value offora the number
H
hydrolysis of bio- High-Energy
of Phosphates Are The phosphorylation
La fosforilación de of glucosa
glucosehacia to glucose 6-phosphate,
glucosa-6-fosfato, the
la primera reac-
Mg2+ ergyque conservation
N el fondo común or energy total capture:
de charge
ATP/ADPcarrierrepulsion protein,
es group
en extremo amino
of adjacent
transfer acid
pequeño, esters
negatively
potential, y
first involvedcharged
rather
reaction in
than of protein
oxygen
“high-energy
glycolysis synthe-
atoms
(Figure bond, ”
18–2), is is highly endergonic
mportant
phosphatephosphates of ATP divides is shown the list in intoTable two 11–1.
groups. An ción de la glucólisis (fig. 18-2), es muy endergónica y no puede pro-
N
suficiente para
H
mantener
H
Designated
un tejido and
sis,activo by
S-adenosylmethionine
to stabilization
sólopreferred~P by
algunos of the reaction
some.
segundos. (active
Thus,and methionine),
products,
ATP
cannot contains
ceder proceed
en
especially
UDPGlc
two
condiciones
phos-
(uri-
high-energy
under physiologic
fisiológicas. phos- conditions.
yhephosphates,
comparative
O –
O exemplified
–
tendency 1. oxidative
ofbyeach the of phosphorylation:
ester
the
OH phosphates
phosphate The greatest quantitative
Hayoftres fuentes
OH
The
principales symbol phate,
dine
de ~P diphosphate
asindicates
resonance
quephate groups
participan glucose),
thathybrids.
the
and
en group
laADP Other
andattached
con- PRPP
“high-energy
contains (5-phosphoribosyl-1-
to
one, thewhereas compounds”
bond, the phosphate in
nsfer
O P to O a suitable
P O CHacceptor 2 O source may be~P in aerobic
obtained from organisms. Free energy comes
GURE
hydrolysis 11–4 at 37°C. High-Energy
Adenosine servación
triphosphate
from dePhosphates
respiratory energía
(ATP) shown
chain o captación
on as the
oxidation Arede
transfer pyrophosphate).
are thiol
to
usingenergía:
an esters
AMP
appropriate
molecular O2
involving
(adenosine coenzyme
acceptor,monophosphate)
results A (eg,
in acetyl-CoA),
transfer
is
Glucose Glucosa of the
of acyl
low-energy
+ Pi → Glucose + Pi → Glucosa type, 6-fosfato
6-phosphate + H2O + H2O (1) (1)
O O C The value C NHfor the hydrolysis of carrier protein, amino acid esters involved in protein synthe-
gnesium complex. Designated
ADP forms
within a similar by ~P
complex
mitochondria with the Mg larger
2+
(Chapterla12). . quantity sinceof free
it is energy.
a normal For ester this linkreason,
(Figure the 11–5).
term
phosphate of ATP divides H H
1.the list into two groups.
2
Fosforilación oxidativa: mayor
sis, fuente cuantitativa(active
S-adenosylmethionine de methionine), UDPGlc
2. Glycolysis:
N
A net formation groupoftransfer two ~P potential,
results from rather than “high-energy bond, ” is(∆G0’(uri-=(∆G+13.8 = +13.8 kJ/mol)
0’ kJ/mol)
phosphates, exemplified The
H symbol H by~P
N theindicates
ester
en phosphates
organismos that the group
aerobios. attached
La energía to the
libre bond,
proviene
Mg2+ onOH transfer the Nformation
to la
de anNoxidación of lactate
appropriate de la
preferred
from
acceptor,
cadena one High-Energy
dineby diphosphate
some.
molecule
results
respiratoria
Thus,
ofusando
in transfer
ATP
glucose, Phosphates
glucose),
contains
ofO2
and two PRPP Are (5-phosphoribosyl-1-
high-energy phos-
OH
phate pyrophosphate).
groups and ADP contains one, whereas the phosphate in
– the larger
generated
quantity
molecular inof two freereactions
dentro de lascatalyzed
energy. For Designated
this by
mitocondrias phosphoglycerate
reason, (cap. the12). byterm ~P
–
nosine triphosphate (ATP) kinase
O O O – NH
shown as 2
and AMP (adenosine
thepyruvate kinase, respectively (Figure 18–2). monophosphate) is of the low-energy H type, Creatine
group transfer 2. glucólisis: potential, unaratherformación than The “high-energy
netasymbol de dos ~P bond, indicates
” is de
depende thatlathe group attached N to the bond, kinase
DP–Oforms P aOsimilar P Ocomplex P O N with
3. The Mg2+
citric
N. since it is a normal ester link (Figure 11–5). P H2N
some.acid cycle: One a~P is generated directly deinglucosa, acceptor, results inC transfer
CH2 O
preferred byformación Thus, deATP lactato contains partir on
two de transfer
high-energy
una molécula to anphos- appropriate of
PTR.inddO 94 2+ O
Mg
O
phate groups the C cycle at
H and
generada H N
C the succinate thiokinase
ADP en contains
dos one,
reacciones
High-Energy
whereas
the step
larger
catalizadas the (Figure
phosphate
quantity
por
Phosphates
17–3).
ofin
fosfoglicerato free energy.
Arethis
For H C reason,
N
NH
H
the term Creatina
H C N
C NH
3/26/2009 8:30:09 PM
N
Designated by ~P rather than “high-energy P N cinasa H2N
3 3

as the O– O–
AMP O–
(adenosine cinasaHmonophosphate)
Phosphagens
H
y piruvato
act as cinasa,isforms
storage ofgroup transfer
theoflow-energy
respectivamente high-energy potential,
(fig. type,
18-2).
phos- CH2
bond, ADP
C NH
” is ATP CH2 C NH
Mg2+ –
. since phateit is3.and elinclude
a normal cicloester delcreatine
ácido cítrico:
link (Figure phosphate, 11–5).
seThe
preferred
symbol
genera
which un by ~P
occurssome. indicates
deinThus,
modo
verte- ATP
that
directo the
contains
grouptwo attached
high-energy
H
to the
C N
(∆Gbond,
phos-
0′ = –12.6 kJ/mol)
H C N
O P O P O P O CH OH OH 3 – 3 –
on
phate transfer groups toand anand ADP
appropriatecontainsacceptor, one, whereas results the inphosphate
transfer of in ADP
2 O
brate skeletal en el muscle,ciclo en heart, el pasospermatozoa,
de la succinato and tiocinasa
brain; (fig.argi-17-3). COO
ATP
COO
CH2
type,(∆G0′ = –12.6 kJ/mol) CH2
O O O
1–4 Adenosine triphosphate C C
H(ATP)Hshown as the
nine phosphate, Los fosfágenos which2+ occurs actúan in como
the
AMP larger
invertebrate (adenosine
formas demuscle.
quantitymonophosphate)
almacenamiento
of
When free energy. For
de
is ofthis the reason,
Creatine low-energy
phosphate the term
3/26/2009 8:30:09 PM
Creatine

omplex. ADP forms a similar complex with Mg . group

sinceof ittransfer
is a normal potential,
ester link rather (Figure than11–5).“high-energy bond, COO– ” is COO–
ATPfosfatoisH rapidly being utilized as a source
de alta energía, e incluyen creatina fosfato, que se encuentra
H energy for muscu- FIGURE 11–7 Transfer of high-energy phosphate between ATP
lar contraction, preferred by some. Thus, ATP contains two high-energy Creatina phos- fosfato Creatina
en el OHmúsculo OH phosphagensestriado, el corazón, permit its espermatozoides
los concentrations toy elbecerebro and creatine.
phate groups and ADP contains one, whereas the phosphate in
de vertebrados, y arginina fosfato, que existe en el músculo de inver-
1–4 Adenosine triphosphate (ATP) shown as the AMP (adenosine monophosphate) 3/26/2009 8:30:09 is PMFIGURA
of the low-energy 11-7 Transferenciatype, de fosfato de alta energía entre ATP y
tebrados. Cuando2+se está utilizando con rapidez ATP como una creatina.
omplex. ADP forms a similar complex with Mg . since it is a normal ester link (Figure 11–5).

3/26/2009 8:30:09 PM

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11 Bender.indd 95 3/26/2009 8:30:09 PM 27/11/09 13:59:13

 Section ii Bioenergetics & the Metabolism of Carbohydrates & Lipids
96 Sección ii Bioenergética y el metabolismo de carbohidratos y lípidos

Para que tenga lugar,

as alatransducer
reacción debe
of acoplarse
o A, B, C, or D, allowing E to serve TABLEcon otra reacción
11–1 Standard Free Energy of Hydrolysis of
Pirofosfatasa
inorgánica
—más exergónica—, como la
rom a wide range of exergonic reactions to an equallyhidrólisis del fosfato terminal del ATP.
Some Organophosphates of Biochemical Importance 2Pi
nge of endergonic reactions or processes, such as bio- 0ʹ
ATP → ADP + P (∆G = -30.5 kJ/mol) (2) ΔG0’
s, muscular contraction, nervous excitation,i and
Pi PPi
ansport. In the living cell, (1)
Cuando they principal high-energy
(2) se acoplan Compound
en una reacción catalizada por hexoci- kJ/mol kcal/mol
diate or carrier compound (designated ~ E in Figure
nasa, la fosforilación de la glucosa procede con facilidad en una re- Acil-CoA
Phosphoenolpyruvate −61.9 −14.8
adenosine triphosphate
acción (AtP).
muy exergónica que en condiciones fisiológicas es irreversi-
sintetasa, etc.

Carbamoyl phosphate −51.4 −12.3

ble. Muchas reacciones de “activación” siguen este modelo.
ATP
-ENERGY PHOSPHATES PLAY A 1,3-Bisphosphoglycerate
(to 3-phosphoglycerate)
−49.3 −11.8

RAL ROLE INLa

ENERGY
adenilil CAPTURE
cinasa (miocinasa)Creatine phosphate −43.1 −10.3
TRANSFER interconvierte nucleótidos adenina
ATP → AMP + PP i
−32.2 ADP
−7.7 X 2 AMP
to maintain livingDicha enzima
processes, allestá presente must
organisms en casiob- todas las células. Cataliza la reac-
ATP → ADP + Pi −30.5 −7.3
Adenilil
ción que sigue:
plies of free energy from their environment. Auto- cinasa

organisms utilize simple exergonic processes; eg, the Glucose 1-phosphate −20.9 −5.0
FIGURA 11-8 Ciclos del fosfato e intercambio de nucleótidos
of sunlight (green plants), the reaction Fe → Fe 2+ ADENILIL
3+
PPi adenina.−19.2 −4.6
CINASA
acteria). On the other hand, heterotrophic organ-
ATP + AMP Fructose
2ADP 6-phosphate −15.9 −3.8
tain free energy by coupling their metabolism to the
wn of complex organic molecules in their environ- Glucose 6-phosphate −13.8 −3.3
Esto permite que:
n all these organisms, ATP plays a central role in the
otros nucleósidos trifosfato participan en
Glycerol 3-phosphate −9.2 −2.2
ence of free energy from 1. El the exergonic
fosfato de alta to the ender-
energía en el ADP se use en la síntesis de la transferencia de fosfato de alta energía
Abbreviations: PPi, pyrophosphate; Pi, inorganic orthophosphate.
ocesses (Figure 11–3).ATP. ATP is a nucleoside triphos- Mediante la enzima nucleósido difosfato cinasa pueden sintetizar-
Note: All values taken from Jencks (1976), except that for PPi which is from Frey and
ntaining adenine, ribose,
2. ElandAMP, three phosphate
formado comogroups.
consecuencia de varias
Arabshahi Values differ between se
(1995).reacciones UTP, GTP
investigators, y CTPona partir
depending de sus difosfatos, por ejemplo,
the precise
actions in the cell, it functions
de activación as the Mg
que
2+
complex ATP, se recupere mediante
comprenden conditions under which the measurements were made.
11–4). refosforilación hacia ADP. NUCLEÓSIDO
DIFOSFATO
importance of phosphates
3. Aumente in intermediary
la concentración metabo- de AMP cuando el ATP se agota
ame evident with the discovery of theunaroleseñal
of ATP, ad- found in the intermediates of glycolysis, have CINASA
G0ʹ values ADP + UTP
y actúa como metabólica (alostérica) para ATP + UDP
diphosphate (ADP), and inorganic el phosphate smaller than that of ATP, while in high-energy phosphates
índice de(P ) in (trifosfato de uridina)
incrementar reacciones
i catabólicas, que a su
is (Chapter 18). the value is higher than that of ATP. The components of this
Todos estos trifosfatos participan en fosforilaciones en la célu-
vez llevan a la generación de más ATP (cap. 20).
latter group, including ATP, la. areDeusually
modo anhydrides (eg, the monofosfato cinasas específicas
similar, nucleósido
1-phosphate of 1,3-bisphosphoglycerate), enolphosphates
catalizan la formación de nucleósido (eg, difosfatos a partir de los mo-
ntermediate Value for the Free
Cuando el aTP forma aMP, se produce phosphoenolpyruvate), and phosphoguanidines (eg,
nofosfatos correspondientes. creatine
y of Hydrolysis of ATP Has Important phosphate, arginine phosphate). The intermediate position of
pirofosfato inorgánico (PPi)ATP allows it to play an important role in energy transfer. The
ergetic Significance NUCLEÓSIDO
El ATP también puede hidrolizarse de manera directa hacia
high free-energy AMP,on hydrolysis of ATP is due to relief ofMONOFOSFATO
change
ndard free energy of conhydrolysis
la liberación of de
a number
PPi (cuadro of 11-1).
bio- Esto sucede,
charge por ejemplo,
repulsion en
of adjacent negatively charged oxygen atoms CINASAS ESPECÍFICAS
lly important phosphates is shown in Table 11–1.
la activación de ácidos grasos de cadena larga An and (cap. 22):
to stabilization ATP + Nucleósido
of the reaction products, especially phos- P
of the comparative tendency of each of the phosphate phate, as resonance hybrids. Other “high-energy compounds”ADP + Nucleósido P P
o transfer to a suitable acceptor may be obtained from are thiol esters involving coenzyme A (eg, acetyl-CoA), acyl
ACIL-CoA
of hydrolysis at 37°C. The value for the hydrolysisSINTETASA of De esta manera, la adenilil cinasa es una monofosfato cinasa espe-
carrier protein, amino acid esters involved in protein synthe-
inal phosphate of ATPATP divides the list+into two groups. cializada.
+ CoA • SH R • COOH sis, S-adenosylmethionine (active methionine), UDPGlc (uri-
ergy phosphates, exemplified by the ester phosphatesAMP dine + R • CO — SCoA
+ PPi diphosphate glucose), and PRPP (5-phosphoribosyl-1-
pyrophosphate). rESuMEN
Esta reacción
NH 2 se acompaña de pérdida de energía libre como
■ En los sistemas biológicos se utiliza energía química para impulsar
calor, lo que asegura N que la reacción de activación irá hacia la dere- procesos vivos.
cha, y se auxilia más por la división hidrolítica del PPi, catalizada
N

Mg2+ por pirofosfatasa inorgánica,

High-Energy Phosphates
una reacción que en sí tiene una ΔG0ʹ
■ Are exergónicas tienen lugar de modo espontáneo, con
Las reacciones
N pérdida de energía libre (ΔG es negativa). Las reacciones endergónicas
grande,
N
de –19.2 kJ/mol. Note que las activaciones Designated por medio byde~P la requieren la ganancia de energía libre (ΔG es positiva) y sólo ocurren
O– O– O–
– vía del pirofosfato dan por resultado la The
pérdida symbol
de dos ~P indicates
más que that the groupseattached
cuando acoplan a to the bond,
reacciones exergónicas.
O P O P O P O CH2 O
de uno, como ocurre cuando se forman ADP on transfer
y Pi. to an appropriate■ acceptor,El ATP actúa results
comoinla “moneda
transfer de of energía” de la célula, al transferir
O O O C
H H
C
the larger quantity of free energy. Forlibre
energía thisderivada
reason,dethe term de potencial de energía superior
sustancias
H H FOSFATASA group transfer potential, ratherhacia thanlas“high-energy
de potencial de bond,
energía” inferior.
is
INORGÁNICA preferred by some. Thus, ATP contains two high-energy phos-
OH OH
PPi + H2O phate groups
2Pi and ADP contains one, whereas the phosphate in
E 11–4 Adenosine triphosphate (ATP) shown as the
rEFErENCIaS
AMP (adenosine monophosphate) is of the low-energy type,
Una combinación
um complex. ADP forms a similar complex withde Mglas2+ reacciones anteriores hace posible que
. since it is a normal ester link de Meis L:
(Figure The concept of energy-rich phosphate compounds: water,
11–5).
el fosfato se recicle y que los nucleótidos adenina se intercambien transport ATPases, and entropy energy. Arch Biochem Biophys
(fig. 11-8). 1993;306:287.

d 94 3/26/2009 8:30:09 PM

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