?4? ????????? (Bioenergetic and Biological Oxidation)

1
????
?4? ?????????(Bioenergetic and Biological
Oxidation)
2
??????????????
???
??
??
ADPPi ATP
????
ADPPi ATP
ADPPi ATP
?????
??????
???
ADPPi ATP
ADPPi ATP
????
???
ADPPi
ADPPi ATP
ATP
??-CoA
ADPPi ATP
?????
????
O2
ADPPi ATP
?????
H2O
NH3
CO2
3
??????????????

• ????,????????????????
• ????,?????????????????,?????????-CoA,????????
• ????,???????,?Krebs??,???????????(TCA)????????????
  CO2,????????NAD?FAD???????,??????????????????

• ????,????????????,?????O2,H2O??,?????????ATP????

-CH? H(??) ?H2O
4
??? ?????? A survey of bioenergetics

• 1.1 Biological Oxidation(????)
• 1.1.1 concept of biological oxidation and its
  significances
• ???????????????????????????????????,????H2O?CO2,??
  ???????,????????????
• ?????(??)???

5
1.1.2 ?????????

• 1948?,Eugene Kenned Albert
  Lehninger??,?????????????????
• ?????????,??????(Mr?5000)????????(??????)
  ????????????????(??H),????????????????????

6
1.1.3 ???????

• ????
• (CH) O2?H2OCO2???
• H2O????????????
• CO2????????????
• ???????,???????

7
1.1.3 ???????

• ????
• (CH) O2?H2O CO2??
• H2O???????????????,H?????????????,???O2????H2O?
• CO2???????????????????
• ???????????????,??????
• ??????????????,????????????????,????????????????

8
1.1.3 ???????
????
????
9
1.1.3 ???????

• ??????????????????????,???????
• ?????????????? ?P 0
• ?????????????? ?V 0
• ? ?H ?U (?????????)

10
1.2 ?????????

• 1.2.1 ?????
• First law of thermodynamic
• ??????
• ?????????,????????????????,??,???????????????
• ????????????686 ?? (1196 kJ/mol)
• ???????????CO2???????????

11
1.2 ?????????

• Second law of thermodynamics
• ?(entropy) ????
• ?????????????????????????????????????????,???
  ??

Maxwell Demon
12
1.2.2 ??? (free energy)
1.2 ?????????

• ????????????????????,??????????????????
• ?G ?H T?S
• ?G - RTlnK
• ?G - nF?E

13
1.2.2.1 ????????????
1.2 ?????????

• ??aA bB cC dD
• ??????G G?? -G??
• ???????(?Gº)
• ???????????1M
• ????25? (298 K) , 1 atm (101325 Pa).

14
????????????

• ???????1.0 M??
• ??????,H?10-7(pH 7.0)
• ?????????????(J/mol)????(kJ/mol)??
• ??????????Gº

15
????????????
???????
?????? ?G 0 ?
16
????????????

• R 1.987 cal/molK 8.315 J/molK
• ? T 25?(298 K)?

? T 37?(310 K)?
17
????????????
18
1.2.2.2 ????

• ?1 ?25? pH 7.0 ?,?0.020 M G-1-P?????????????,????
  ?,????????? G-1-P 0.001 M G-6-P
  0.019 M
• ??????????

???? G-1-P G-6-P
?
19
1.2.2.2 ????

• ?2 ?25? pH 7.0 ?,??????G-6-P,??Glucose
  ???,?????,G-6-P????0.1 M, ???G-6-P?????????0.05?
• ?(1)G-6-P???Keq
• (2)???????Gº
• (3)??????????G-6-P??Keq
• (4)??????????G-6-P???Gº
• ? ?????G-6-P H2O G Pi

(1)
20
1.2.2.2 ????
(2)
?Gº - RT lnkeq -5707 log 199.8
-3138 cal/mol -13130 J/mol
???????????????????????
(3)
(4)
?Gº - RT lnkeq -5707 log 510-3
3138 cal/mol 13130 J/mol
21
1.2.2.3 ????????????

• ??????????????????

?? A B 63 kJ/mol
????????? A B 29.3 kJ/mol
x y
xy
xy??????????????
C D C-D 12.55 kJ/mol
xy
x y
22
1.2.2.3 ????????????

• ?Gº? ?G1º ?G2º
• Keq? Keq1Keq2

?Gº?-5707 lg Keq?
23
1.2.2.3 ????????????

• ??3
• ?? ATP H2O ADP Pi ?Gº
  -30.54 kJ/mol
• G-6-P H2O G Pi
  ?Gº -13.35 kJ/mol
• ? G ATP G-6-P ADP ?Gº
  ?

????????
ATP H2O ADP Pi ?Gº -30.54
kJ/mol
)
G Pi G-6-P H2O ?Gº 13.35 kJ/mol
ATP H2O G Pi ADP Pi G-6-P
H2O
ATP G ADP G-6-P
? ?Gº -17.19 kJ/mol
24
1.3 ?????????? p115

• 1.3.1 ?????????
• ??(redox pair) ????????????????,???????
• ???(?)/???(?)

Cu2/Cu ? Zn2/Zn
EºCu2/Cu 0.34 V EºZn2/Zn -0.763 V
25
1.3 ??????????
????????,????????????????
EºCu2/Cu 0.34 V EºZn2/Zn -0.763 V
26
1.3 ??????????

• 1.3.2 ?????????????,???????????,???????????????E
  ?
• For example
• A? B? A? B?
• Cu2 Zn Cu
  Zn2

???
???
??????
??????
??
??
27
??? ?Eº E?º E-?º
1.3 ??????????
???????????????????
???????,????????????
28
???????,???????????????
????????, ?E 0
?
29
1.3.3 ??????????
1.3 ??????????
2.303 RT logkeq nF?Eº
? ?Gº -nF ?Eº - 46.124 ?Eº
??????????????????
30
1.3 ??????????

• ??4
• ??????(LDH)????????,????????NAD?NADH,??
  ???????????,????????????????

????? pyruvate NADHH lactate
NAD ?????
pyruvate 2e- 2H lactate
Eº -0.19 V NAD 2e- 2H
NADHH Eº -0.32 V
????Eº E?º E-?º -0.19 (-0.32) 0.13 V
31
1.3 ??????????
??Eº 0.13 V ???? ?Gº -nF ?Eº
? ?Gº -nF ?Eº -2 23063 0.13
-5969 (cal/mol) -24974 (J/mol)

• ????????,?????????????,???????

32
(No Transcript)
33
??? ?????(High energycompounds)

• 2.1 Concepts
• ?????????????????????????????
• ?????????????????????????????,????

34
High energy compounds

• ?????,??????????????????????
• ?????5000?/mol(20.92 kJ/mol)??????????????????????

35
2.2 Types of high energy compounds
???????
????
??????
????
????????
??????
????
????
36
2.2.1 ????(OP)
(1)???????
????
3-???????
?Gº -11.8 kCal/mol -49.3 kJ/mol
?Gº -10.1 kCal/mol -42.2 kJ/mol
37
(1)???????
2.2.1 ????(OP)
?????
?????
??????
38
(2)??????
2.2.1 ????(OP)
???
ATP(?????)
?Gº-7.3 kCal/mol -30.5 kJ/mol
???
39
(3)????????
2.2.1 ????(OP)
????????
?Gº -14.8 kCal/mol -61.9 kJ/mol
40
2.2.2 ????
H
????
?????
?Gº -10.3 kCal/mol -43.1 kJ/mol
?Gº -7.7 kCal/mol -32.2 kJ/mol
??????????????????????
41
2.2.3 ????
????A
3-????-5-????
42
2.2.4 ????
S-??????
???????
43
2.3 Significance of ATP in bioenergys
????
p41
44
2.3 Significance of ATP in bioenergys

• 2.3.1 ATP????????
• ATP-ADP???????????
• ADP???????????
• ATP???????????
• ??????????????????ATP-ADP???????
• ATP?????????????????,???????,???AMP

45
2.3 Significance of ATP in bioenergys
???(??)
?? ???? (????) ???? ??
ATP ADP
???(??)
???(?????)
p
??(???)
??(??????)
??(????)
46
2.3 Significance of ATP in bioenergys

• ATP?????????
• ATP???????????????

47
2.3.2 ATP????????????????
2.3 Significance of ATP in bioenergys

• Hydrolysis of each of the two phosphoanhydride
  bonds in ATP releases a large amount of free
  energy
• ?Gº -30.5 kJ/mol
• ?G -50 to -65 kJ/mol

48
2.3 Significance of ATP in bioenergys
2.3.2 ATP????????????????
??5
????

• ?? ATP Glucose ADP G-6-P
• ?G1º -4.0 kcal/mol
• G-6-P?? G-6-P H2O Glucose
  Pi
• ?G2º -3.3 kcal/mol
• ??? ATP H2O ADP Pi
  ??G1º?Keq

G-6-P???
49
2.3 Significance of ATP in bioenergys
2.3.2 ATP????????????????

• ?????????,?? ATP H2O ADP Pi
• ?????????
• ATP Glucose ADP
  G-6-P
• ) G-6-P H2O
  Glucose Pi
• ATP Glucose G-6-P H2O ADP G-6-P
  Glucose Pi
• ATP H2O ADP Pi
• ? ?Gº ?G1º ?G2º (-4.0) (-3.3)
• -7.3 kcal/mol -30.5
  kJ/mol
• ?????? Keq 1.631 105

50
2.3 Significance of ATP in bioenergys
2.3.2 ATP????????????????

• ??????????
• ?????
• ATP 2.25 mM
• ADP 0.25 mM
• AMP 0.01 mM
• Pi 1.65 mM
• ? ?G -51.8 kJ/mol

?Gº -7.3 kcal/mol -30.5 kJ/mol
51
2.3 Significance of ATP in bioenergys
2.3.2 ATP????????????????
?????????????????????
52
2.3 Significance of ATP in bioenergys
2.3.2 ATP????????????????
53
Chemical basis of high free energy release of ATP
hydrolysis

• Relief of electrostatic repulsion(????) in ATP
• The phosphoanhydride bonds(???) is easy
  hydrolyzed than other phosphate ester bonds(???)
• Pi is more stabilized by resonance(??) not
  possible in ATP
• ADP2- immediately ionizes to ADP3- (ADP2-
  decreases)
• ?G0 also depends on Mg2 and Ca2.

54
2.4 ????????Storage of high energic phosphate
bounds

• ATP is not a long-term storage form of free
  energy.
• Bank currency

????????(phosphocreatine)
????
??????????(phosphoarginine)
???????
55
2.4 ????????
????
??
???????????20 mM,??????ATP???10?
H
?????
56
2.5 ATP??????

• ATP???????????????Gº??????????????
• ATP???????????????????????
• ? ATP AMP 2ADP ?Gº ? 0
• ATP??????????????????????????
• ????????ATP?????????????

57
2.5 ATP??????
?????
ATP
dATP
CTP
dGTP
UTP
ATP
ATP
ATP
ATP
ATP
GTP
CTP
GTP
dCTP
UTP
dTTP
????
???
??
RNA
DNA
58
2.5 AMP???????

• ?ATP????????,ATP??????????????????
• ?????????????
• ?????????????,???????
• ATP H2O AMP PPi ?Gº -7.7 kCal/mol
• PPi H2O 2Pi ?Gº
  -6.9 kCal/mol

ATP 2H2O AMP 2Pi ?Gº-14.6
kCal/mol - 61.1 kJ/mol
59
2.6 ????????

• ??
• ?????0lt ??lt1
• ?????

???????Pi?????,?Pi??????ATP?????????
60
??? ????
61
??? ????
NAD(P)???
62
3.1 ???????????

• ?????????????
• NAD?FAD????????,??H???,???NADH?FADH2???????????(
  H?O??),??ATP???(??????90????)?
• NADP????????H???,????NADPH??????????,???????H??
  ?(H?C??)?

63
3.1 ???????????

• ??NAD NADH ? 10-5 M (0.01mM),
• NAD /NADH 700
• ??NADP NADPH ? 10-6 M (0.001mM),
  NADP/NADPH 0.014
• The high ratio of NAD /NADH favors
  metabolite oxidation, while keeping their
  NADP/NADPH ratio near 0.01, which favors
  metabolite reduction.

64
3.1 ???????????

• ????????????????
• ??????????????
• ??????????
• ????????????

65
3.2 ????????????

• ???????NADH????????????ATP???
• ??????NADH?NADPH??????
• ? ??????(Shuttle System)

66
????(Shuttle System) p139

• 3.2.1 ?????? (phosphoglycerol shuttle)

????
?????
??-3-?????
??????
67
????(Shuttle System)
3.2.2 ???-????????? Malate-Aspartate
Shuttle
????
68
????(Shuttle System)
p140
69
3.2.3 ????????
????(Shuttle System)

• ??????????????????????
• ???????NADP??????????,??NADPH
• ??????????????????NAD /NADH?NADP /NADPH??????

70
3.2.4 ????

• ????FAD?FMN
• ????????,????
• ????????,????????
• ????????????????

71
3.2.4 ????
????
72
3.2.4 ????
73
3.2.5 ?????????ATP???NAD(P)??
(CH)
74
??? ??????????
75
4.1 ???????????(??)
76
4.1 ???????????(??)

• (1)??(??)(oxidation)
• RCHO 1/2O2 ? RCOOH
• (2)??(dehydrogenation)
• RCH2OH 2H ? RCHO
• CH3CHO H2O ? ?CH3CH(OH)(OH)?
• ? CH3COOH 2H
• (3)???(deelectronation)
• Fe2 -e ? Fe3

????
????
77
4.2 CO2?????

• ???????????(decarboxylation)???
• ?????????????
• ?-decarboxylation
• ?-decarboxylation
• ?????????????
• simple decarboxylation
• oxidative decarboxylation

78
?????????

• ?-??
• R-CH(NH2)-COOH?RCH2NH2 ? CO2
• ?-????
• CH3COCOOH NAD CoASH ? CH3COSCoA
• NADHH CO2
• ?-??
• HOOCCO-CH2COOH ? CH3COCOOH CO2
• ?-????
• HOOCCH(OH)-CH2COOH NADP ?
• CH3COCOOH CO2 NADPHH

??????
???????
??????
????
79
4.3 ?????????

• ?????????????????????
• ???????????????
• ??????????????

H2O
?????
M2H
???
???
???????
M
?????
½ O2
80
4.3.1 ????????????

• 4.3.1.1 ???????????
• ?????
• ???????????????
• ???????????????
• ?????????????

H2O
???VC
2Cu2
???
2Cu
VC
½ O2
2H
81
4.3.1 ????????????

• 4.3.1.2 ?????????????
• ???????????,?????????
• ???????????,??H2O2
• H2O2???????

H2O2
FAD
M2H
????? ??????
?????
H2O ½ O2
FADH2
M
O2
82
4.3.2 ???????????

• ?????????
• ?????????????????????????

4.3.2.1 ???? ?????????????? 4.3.2.2 ????
???????,??NAD??????????????????