Acoplamiento de Reacciones

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Acoplamiento de Reacciones
Juan Pablo Damián
Bioquímica –Curso BMC – 2009
Facultad de Veterinaria
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ATP: moneda energética universal en todas
las células
• La hidrólisis del ATP per se normalmente no consigue nada
excepto la liberación de calor.
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ATP: moneda energética universal en todas
las células
• La hidrólisis del ATP per se normalmente no consigue nada
excepto la liberación de calor.
ATP, puede transferir energía desde
compuestos fosfato de alta energía
producidos en el catabolismo hasta
compuestos de baja energía, convirtiéndolos
en especies más reactivas.
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Una reacción termodinámicamente desfavorable
(endergónica) puede ser posible?
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Una reacción termodinámicamente desfavorable
(endergónica) puede ser posible?
Sí, gracias al acoplamiento de reacciones
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Una reacción termodinámicamente desfavorable
(endergónica) puede ser posible?
Sí, gracias al acoplamiento de reacciones
secuenciales a través de un intermediario común.
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6
ATP
CH2OH
ADP
6
H
4
OH
5
H
OH
3
H
H
Mg2+
4
OH
2
HEXOQUINASA
OH
OH
H
OH
3
H
Glucosa (G)
H
1
OH
2
OH
Glucosa 6 Fosfato (G6P)
G + Pi
Compuesto
rico en energía
5
H
1
CH2OPO3=
 G6P + H2O
ATP + H2O  ADP + Pi
G + ATP  G6P + ADP
G´= 13,8 kJ/mol
G´= - 30.5 kJ/mol
G´= - 16.7 kJ/mol
Fosforila la glucosa para las reacciones que tienen lugar en casi todas las células.
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… hasta compuestos de baja energía como
la glucosa…
6
ATP
CH2OH
ADP
6
H
4
OH
5
H
OH
3
H
H
Mg2+
1
4
OH
2
HEXOQUINASA
OH
OH
5
H
OH
3
H
Glucosa (G)
H
2
1
OH
OH
Glucosa 6 Fosfato (G6P)
G + Pi
Compuesto
rico en energía
H
CH2OPO3=

ATP + H2O
G + ATP

G6P + H2O
G´= 13,8 kJ/mol
ADP + Pi
G´= - 30.5 kJ/mol
G6P + ADP
G´= - 16.7 kJ/mol

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Glucosa+ Pi  Glucosa 6-P + H2O
∆G’°= 13.8 kJ/mol
El carácter aditivo de los ∆G permite que una reacción
endergónica sea dirigida por una reacción exergónica bajo
las condiciones adecuadas.
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Glucosa+ Pi  Glucosa 6-P + H2O
ATP + H2O  ADP + Pi
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∆G’°= 13.8 kJ/mol
∆G’°= - 30.5 kJ/mol
Glucosa+ Pi  Glucosa 6-P + H2O
ATP + H2O  ADP + Pi
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∆G’°= 13.8 kJ/mol
∆G’°= - 30.5 kJ/mol
Las ∆G’° son aditivas
Glucosa+ Pi  Glucosa 6-P + H2O
ATP + H2O  ADP + Pi
Glucosa + ATP  Glucosa 6-P + ADP
∆G’°= 13.8 kJ/mol
∆G’°= - 30.5 kJ/mol
∆G’°= - 16.7 kJ/mol
La reacción global es exergónica
Los de cambios de energía libre son aditivos y permiten que una
reacción endergónica sea impulsada por una reacción
exergónica bajo condiciones apropiadas.
Las dos reacciones están acopladas por medio de su
intermediario común.
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El ATP cómo se sintetiza?
-O
O
ADP
ATP
-O
O
C
C
1
H
C
2
3
1
OPO3=
CH2
C
2
PIRUVATO KINASA
3
Fosfoenolpiruvato
(PEP)
CH3
Piruvato
(PIR)
PEP +H2O
Compuesto muy
rico en energía
O
ADP + Pi

Pi + PIR
 ATP +H2O
PEP + ADP  PIR + ATP
G´= - 61.9 kJ/mol
G´= + 30.5 kJ/mol
G´= - 31.4 kJ/mol
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ÄG´° de hidrólisis (kJ/mol)
Fosfoenolpiruvato
Fosfocreatina
1,3-Bisfosfoglicerato
-25 KJ/mol
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Compuestos de
alta energía
Compuestos de
baja energía
Síntesis del ATP
-O
O
ADP
C
C
2
3
-O
O
C
Mg+2 K+
1
H
ATP
1
OPO3=
CH2
C
2
PIRUVATO KINASA
3
Fosfoenolpiruvato
(PEP)
CH3
Piruvato
(PIR)
PEP +H2O
Compuesto muy
rico en energía
O
ADP + Pi

Pi + PIR
 ATP +H2O
PEP + ADP  PIR + ATP
G´= - 61.9 kJ/mol
G´= + 30.5 kJ/mol
G´= - 31.4 kJ/mol
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ATP transfiere energía desde compuestos muy
ricos en energía hasta…
-O
O
ADP
ATP
-O
O
C
C
1
H
C
2
3
1
OPO3=
CH2
C
2
PIRUVATO KINASA
3
Fosfoenolpiruvato
(PEP)
CH3
Piruvato
(PIR)
PEP +H2O
Compuesto muy
rico en energía
O
ADP + Pi

Pi + PIR
 ATP +H2O
PEP + ADP  PIR + ATP
G´= - 61.9 kJ/mol
G´= + 30.5 kJ/mol
G´= - 31.4 kJ/mol
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… hasta compuestos de baja energía como
la glucosa…
6
ATP
CH2OH
ADP
6
H
4
OH
5
H
OH
3
H
H
Mg2+
4
OH
2
HEXOQUINASA
OH
OH
H
OH
3
H
Glucosa (G)
H
2
1
OH
OH
Glucosa 6 Fosfato (G6P)
G + Pi
Compuesto
rico en energía
5
H
1
CH2OPO3=
 G6P + H2O
ATP + H2O  ADP + Pi
G + ATP  G6P + ADP
G´= 13,8 kJ/mol
G´= - 30.5 kJ/mol
G´= - 16.7 kJ/mol
pdfMachine
Is a pdf
that producesque
qualitytienen
PDF files with
ease!en casi todas las células.
cebaProduce
la glucosa
para
laswriter
reacciones
lugar
quality PDF files in seconds and preserve the integrity of your original documents. Compatible across
nearly all Windows platforms, if you can print from a windows application you can use pdfMachine.
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… hasta compuestos de baja energía como
la glucosa…
6
ATP
CH2OH
ADP
6
H
4
OH
5
H
OH
3
H
H
Mg2+
1
4
OH
2
HEXOQUINASA
OH
OH
5
H
OH
3
H
Glucosa (G)
H
2
1
OH
OH
Glucosa 6 Fosfato (G6P)
G + Pi
Compuesto
rico en energía
H
CH2OPO3=

ATP + H2O
G + ATP

G6P + H2O
G´= 13,8 kJ/mol
ADP + Pi
G´= - 30.5 kJ/mol
G6P + ADP
G´= - 16.7 kJ/mol

pdfMachine
Is a pdf
that producesque
qualitytienen
PDF files with
ease!en casi todas las células.
cebaProduce
la glucosa
para
laswriter
reacciones
lugar
quality PDF files in seconds and preserve the integrity of your original documents. Compatible across
nearly all Windows platforms, if you can print from a windows application you can use pdfMachine.
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EJERCICIO
Consideren estas dos reacciones de la Glucólisis:
1) GAP + NAD+ + Pi  1,3BPG + NADH + H+
ÄGº’ = + 6.3 kJ.mol-1
2) 1,3-BPG + ADP  3-PG + ATP
ÄGº’ = -18.8 kJ.mol-1
La suma de las dos reacciones es :
GAP + NAD+ +ADP + Pi

3PG + NADH + H+ + ATP
ÄGº’ = ÄGº’1 + ÄGº’2 = + 6.3 + ( -18.8) = -12.5 kJ.mol -1
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EJERCICIO
Consideren estas dos reacciones de la Glucólisis:
1) GAP + NAD+ + Pi  1,3BPG + NADH + H+
ÄGº’ = + 6.3 kJ.mol-1
2) 1,3-BPG + ADP  3-PG + ATP
ÄGº’ = -18.8 kJ.mol-1
La suma de las dos reacciones es :
GAP + NAD+ +ADP + Pi  3PG + NADH + H+ + ATP
ÄGº’ = ÄGº’1 + ÄGº’2 = + 6.3 + ( -18.8) = -12.5 kJ.mol -1
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•
•
•
•
Responder
¿Qué compuestos ricos en energía intervienen?
¿Son reacciones acopladas?
¿Cuál es el reactivo intermediario común?
¿Qué compuesto se sintetiza, consumiendo energía?
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Soluciones
1,3BPG y ATP
Es un caso de acoplamiento de reacciones
El intermediario común es el 1,3BPG
Se oxida el GAP a expensas del NAD+, que se
reduce
• Se sintetiza ATP a partir de ADP y Pi
•
•
•
•
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Características de las reacciones acopladas
Implican la ruptura de enlaces ricos en energía del ATP o de derivados fosforilados
de azúcares.
Son bastante comunes en las rutas metabólicas y generalmente implican la
transferencia de grupos fosforilo.
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Acoplamiento
de reacciones
• El carácter aditivo de los ∆G permite que
una reacción endergónica sea dirigida por
una reacción exergónica bajo las
condiciones adecuadas.
• Este fenómeno es la base termodinámica
del metabolismo celular.
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