Download H - Bonham Chemistry

Chemistry 2100
Chapter 28
Carbohydrate Catabolism
• glycolysis: glucose
• TCA Cycle: acetyl CoA
pyruvate
acetyl CoA
CO2 + NADH / FADH2
• oxidative phosphorylation: NADH / FADH2
ATP
Glycolysis
H
C
H
OH
HO
H
O
AT P ADP
H
H
OH
H
OH
CH 2 OH
gluc ose
H
HO
he xokinase
M g +2
H
C
O
H
OH
OH
H
OH
-2
CH 2 O PO 3
gluc ose -6-phosphat e
OH
O
H
H
C
isome r ase
HO
H
(e ne diol)
H
OH
H
OH
-2
CH 2 O PO 3
fr uc tose -6-phosphate
H
C
H
OH
HO
H
O
AT P ADP
H
H
OH
H
OH
CH 2 OH
gluc ose
H
HO
he xokinase
M g +2
H
C
O
H
OH
OH
H
OH
-2
CH 2 O PO 3
gluc ose -6-phosphat e
OH
O
H
H
C
isome r ase
HO
H
(e ne diol)
H
OH
H
OH
-2
CH 2 O PO 3
fr uc tose -6-phosphate
H
C
H
OH
HO
H
O
AT P ADP
H
H
OH
H
OH
CH 2 OH
gluc ose
H
HO
he xokinase
M g +2
H
C
O
H
OH
OH
H
OH
-2
CH 2 O PO 3
gluc ose -6-phosphat e
OH
O
H
H
C
isome r ase
HO
H
(e ne diol)
H
OH
H
OH
-2
CH 2 O PO 3
fr uc tose -6-phosphate
H
C
H
OH
HO
H
O
AT P ADP
H
H
OH
H
OH
CH 2 OH
gluc ose
H
HO
he xokinase
M g +2
H
C
O
H
OH
OH
H
OH
-2
CH 2 O PO 3
gluc ose -6-phosphat e
OH
O
H
H
C
isome r ase
HO
H
(e ne diol)
H
OH
H
OH
-2
CH 2 O PO 3
fr uc tose -6-phosphate
H
C
H
OH
HO
H
O
AT P ADP
H
H
OH
H
OH
CH 2 OH
gluc ose
H
HO
he xokinase
M g +2
H
C
O
H
OH
OH
H
OH
-2
CH 2 O PO 3
gluc ose -6-phosphat e
OH
O
H
H
C
isome r ase
HO
H
(e ne diol)
H
OH
H
OH
-2
CH 2 O PO 3
fr uc tose -6-phosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
phosphofructokinase
hexokinase
Mg
+2
H
O
AT P ADP
HO
H
H
O
H
OH
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
hexokinase
Mg +2
H
O
AT P ADP
HO
H
H
O
H
OH
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
hexokinase
Mg +2
H
O
AT P ADP
HO
H
H
O
H
OH
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
HO
hexokinase
Mg +2
H
O
AT P ADP
H
H
•
•
H
O
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
OH
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
HO
hexokinase
Mg +2
H
O
AT P ADP
H
H
•
•
H
O
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
OH
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
HO
hexokinase
Mg +2
H
O
AT P ADP
H
H
•
•
H
O
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
OH
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
HO
hexokinase
Mg +2
H
O
AT P ADP
H
H
•
•
H
O
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
OH
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
-2
CH 2 O PO 3
O
HO
CH 2 O PO 3-2
HO
hexokinase
Mg +2
H
O
AT P ADP
H
H
•
•
H
O
•
aldolase
H
dihydroxyacetone
phosphate
(en ed iol)
H
OH
H
-2
CH 2 O PO 3
fru ctose-1,6-dip hosphate
H
•
O
OH
-2
CH 2 O PO 3
glyceraldehyde-3-p hosphate
O
H
H
C
H
O
C
OH
CH2O
glyceraldehyde
3-phosphate
+
PO3-2
NH 2
dehydrogenase
N
AD
HPO4-2
-2
O
C
NAD +
H
O PO3
OH
H O
C
H
+
••
CH2O
1,3-bisphospho
glycerate
-2
PO3
N
AD
NADH
NH 2
O
H
C
O
-2
PO3
O
A DP A TP
OH
CH2 O
-2
PO3
1,3
bisphospho
gly
ceric
a cid
1 ,3d ip h osp ha t e
glycerate
k ina se
Mg +2
H
C
O H
O
mut a se
OH
CH2 O
gly ceric a cid
3- p ho sph a t e
-2
PO3
H
C
OH
O
CH2 O
gly ceric a cid
2- p ho sph a t e
-2
PO3
H
O
H
C
O
-2
PO3
O
A DP A TP
OH
CH2 O
-2
PO3
gly bisphospho
ceric a cid
1,3
1 ,3- d ip h osp ha t e
glycerate
k ina se
Mg +2
H
C
O H
O
mut a se
OH
CH2 O
gly ceric a cid
3- p ho sph a t e
-2
PO3
H
C
OH
O
CH2 O
gly ceric a cid
2- p ho sph a t e
-2
PO3
H
O
H
C
O
-2
PO3
O
A DP A TP
OH
CH2 O
-2
PO3
glybisphospho
ceric a cid
1,3
1 ,3- d ip h osp ha t e
glycerate
k ina se
Mg +2
H
C
O H
O
mut a se
OH
CH2 O
gly
ceric a cid
3-phospho
3- p ho sph a t e
glycerate
-2
PO3
H
C
OH
O
CH2 O
gly ceric a cid
2- p ho sph a t e
-2
PO3
H
O
H
C
O
-2
PO3
O
A DP A TP
OH
CH2 O
-2
PO3
glybisphospho
ceric a cid
1,3
1 ,3- d ip h osp ha t e
glycerate
k ina se
Mg +2
H
C
O H
O
mut a se
OH
CH2 O
gly
ceric a cid
3-phospho
3- p ho sph a t e
glycerate
-2
PO3
H
C
OH
O
CH2 O
gly
ceric a cid
2-phospho
2- p ho sph a t e
glycerate
-2
PO3
H
O
H
C
O
-2
PO3
O
A DP A TP
OH
CH2 O
-2
PO3
gly ceric a cid
1 ,3- d ip h osp ha t e
k ina se
Mg +2
H
C
O H
O
mut a se
OH
CH2 O
gly ceric a cid
3- p ho sph a t e
-2
PO3
H
C
OH
O
CH2 O H
2-phospho
gly
ceric a cid
2p ho sph a t e
glycerate
-2
PO3
O
C
eno lase
H
( - H2O)
-2
O OPO3 OH
C A DP
A TP
O PO3- 2
OH
CH2 O
O
-2
POCH
3 2
gly ceric a cid
1 ,3- d ip h osp ha t e
k ina se
Mg +2
C
AD P ATP
H
k in ase
Mg +2
O O
H
OH
CH2 O
gly ceric a cid
3- p ho sph a t e
OH
C
mut a se
O H
-2
POCH
3 2
O
H
C
OH
O
CH2 O H
2-phospho
gly
ceric a cid
2p ho sph a t e
glycerate
-2
PO3
O
C
eno lase
OH
AD P ATP
O PO3- 2
( - H2O)
CH 2
O
k in ase
Mg +2
C
OH
O H
CH 2
O
C
eno lase
OH
AD P ATP
O PO3- 2
( - H2O)
CH 2
O
k in ase
Mg +2
C
OH
O H
CH 2
O
C
eno lase
OH
AD P ATP
O PO3- 2
( - H2O)
CH 2
O
k in ase
Mg +2
C
OH
O H
CH 2
O
C
eno lase
OH
AD P ATP
O PO3- 2
( - H2O)
CH 2
O
k in ase
Mg +2
C
OH
O
C
O H
CH 2
OH
O
CH2
H
pyruvic
pyruvateacid
Anaerobic Glycolysis
O
C
OH
O
NAD +
NAD H
O
CH3
pyruvic acid
pyruvate
+
H
C
OH
OH
H
H
HO
CH3
(–)-lactic
acid
lactic acid
Fermentation
O
C
OH
C O2
O
CH 3
pyruvic acid
pyruvate
deca rbo x y la se
H
O
CH 3
acetaldehyde
acetaldehyde
H
N A D+
N A DH
+
H
H
OH
CH 3
ethanol
ethanol
TriCarboxylic Acid Cycle Prep
O
C
OH
N AD+
O
CH 3
pyruvic a cid
pyruvate
+
H S
CoA
N ADH
S
CoA
O
+
(- H )
CH 3
a cet y l C oA
+
CO 2
• http://highered.mcgrawhill.com/sites/0072507470/student_view0/
chapter25/animation__how_glycolysis_wo
rks.html
Fatty Acids and Energy
Fatty acids in triglycerides are the principal storage
form of energy for most organisms.
– Hydrocarbon chains are a highly reduced form of carbon.
– The energy yield per gram of fatty acid oxidized is greater
than that per gram of carbohydrate oxidized.
Energy
Energy
-1
(k cal• mol ) (kcal• g -1)
C6 H1 2 O6 + 6 O2
Glucose
CH3 (CH2 ) 1 4 COOH + 2 3 O2
Palmitic acid
6 CO2 + 6 H2 O
686
3.8
1 6 CO2 +1 6 H2 O 2,340
9.3
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
O
CH3 (CH2 )12 CH2
HS CoA
thiokinase
CH2
C OH
2 ATP
1
2 ADP
O
CH3 (CH2 )12 CH2
CH2
C
S
CoA
FAD
2
dehydroge nase
FAD H2
O
CH3 (CH2 )12 CH
CH
C
S
CoA
H2O
hydrase
3
OH
CH3 (CH2 )12
CH
O
CH2
C S
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
back to 2
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
-oxidation
OH
CH 3 (CH 2 )12
back to 2
O
CH
CH 2
C S
CoA
NAD +
4
dehydroge nase
NAD H
O
CH 3 (CH 2 )12
O
C
CH 2
thiolase
HS
C S
C
5
CoA
O
CH 3 (CH 2 )12
CoA
O
S
CoA
+
CH 3
C S
repeat 6 time s
CoA
O
CH 3 (CH 2 ) 14
C S
CoA + 7 H2 O + 7 FAD + 7 NAD
+
+ 7 HS
O
8 CH 3 C S
+
CoA + 7 FAD H2 + 7 NAD H + 7 H
CoA
Energy Yield on -Oxidation
• Yield of ATP per mole of stearic acid (C18).
Step Chemical Step
Happ ens ATP
1
Activation (stearic
acid -> stearyl CoA)
Once
-2
2
Oxidation (acyl CoA —>
trans-enoyl CoA)
produces FA D H 2
8 times
16
4
Oxidation (hydroxy8 times
acyl CoA to ketoacyl
CoA ) produ ces N A D H +H +
24
Oxidation of acetyl CoA
9 times
by the common metabolic
path w ay, etc.
TOTAL
108
146
Ketone Bodies
• Ketone bodies: Acetone, -hydroxybutyrate, and
acetoacetate;
– Are formed principally in liver mitochondria.
– Can be used as a fuel in most tissues and organs.
• Formation occurs when the amount of acetyl CoA
produced is excessive compared to the amount of
oxaloacetate available to react with it and take it into the
TCA; for example:
– Dietary intake is high in lipids and low in carbohydrates.
– Diabetes is not suitably controlled.
– Starvation.
Ketone Bodies
O
2 CH3 C-SCoA
Acetyl-CoA
HS-CoA
O
O
CH3 CCH2 C-SCoA
Acetoacetyl-CoA
O
NADH
OH
CH3 -C-CH2 -COOCH3 -CH-CH2 -COOA cetoacetate
NAD+ + H+ -Hyd roxybutyrate
CO2
O
CH3 -C-CH3
Acetone
Protein Catabolism