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Dr. V. SivaPrabodh
MD.
Professor
High energy phosphates &Low energy phosphates:
Compound
Phosphoenolpyruvate -14.8
Carbamoyl phosphate -12.3
1,3 – Bisphosphoglycerate -11.8
Creatine phosphate -10.3
ATP ADP + Pi -7.3
ADP AMP + Pi -6.6
Pyrophosphate -6.6
Glucose 1-phosphate -5.0
Fructose 6 –phosphate -3.8
AMP -3.4
Glucose 6 –phosphate -3.3
Glycerol 3-phosphate -2.2
Kcal/mol
-7.3ATP ADP +Pi
Adenosine Triphosphate (ATP)
Importance of Adenosine Triphosphate (ATP)
 ATPservesasthegeneral "freeenergy currency" for
virtually all cellular processes.
 It isadirect sourceof energy for cell motility, muscle
contraction, and thespecific transport of substances
acrossmembranes.
 ATPisasourceof phosphateenergy for synthesisof the
other nucleosidetriphosphatesviathereaction:
ATPisalso an allosteric effector of many enzymes.
cytochromes:
Protein-bound :- Heme containing carriers
 Cytochromesconstituteafamily of
colored proteinscontaining the
Hemeprosthetic group
Nature of e- Carriers:
Protein-bound carriers :- Iron-sulphurcenters
 Feion iscoordinated with thesulphursof cysteine
residuesand inorgnic sulphur atoms.
Nature of e- Carriers:
Mobile carriers :- Coenzyme Q
 CoenzymeQ: small hydrophobic moleculeand theonly
onethat isnot apart of protein.
Organization of carriers in ETC:
Complex I
NADH dehydrogenase complex :
Largest Respiratory enzyme complex
> 40 polypeptide chains
Bound FMN
At least 7 iron-sulfur centers
Electron transfer From NADH to Co Q
Blocked by Rotenone and Amytal
Complex II
SuccinateDehydrogenase:
It isapoint of entry of electronsfrom FADH2
produced by theenzymesuccinatedehydrogenasein
thecitric acid cycle.
 FAD asProsthetic group
 Iron-sulfur proteins
 Electron transfer From FADH2 to Co Q
 Thus, both complexesI and II donatetheir electrons
to thesameacceptor, coenzymeQ.
CoenzymeQ :
 Benzoquinonelinked to 10 isopreneunits
 It hastheability to accept electronsin pairsand passthem one
at atimethrough asemiquinoneintermediateto Complex III.
Thiscycleisreferred to astheQ cycle.
 Electron transfer From Complex I or II to Complex III
Cytochromec : Thissmall mobileprotein accepts
e- from Complex III and shuttlesthem to Complex IV
Complex III
Cytochromeb-c1 complex :
It isaDimer
 Each monomer has:
3 Hemesbound to cytochromes
1 Iron-sulfur protein
 Electron transfer From Co Q to cytochromec
 Cytochromec then transferse- to thecomplex IV
 Blocked by Antimycin A
Complex IV
Cytochromeoxidasecomplex :
 Dimer
 Each monomer has:
13 Different polypeptidechains, including
2 Cytochromesaand a3 and
2 Cu atoms
 AcceptsoneElectron at atimefrom Cytochromec and
passesthem four at atimeto Oxygen
 Blocked by Cyanide, Azide, and Carbon monoxide
Organization of carriers in ETC:
Oxidative Phosphorylation
 Chemical coupling
 Chemiosmotic hypothesis
- proposed by Mitchel
- dependent on proton gradient.
Chemiosmotic Coupling:
 1. Theactivetransport of electronspumpsprotonsout of the
mitochondrial matrix into theinter membranespace.
 2. An electrochemical gradient of protonsiscreated, outsidethe
inner mitochondrial membranethan inside.
Theprotonson theoutsidehaveathermodynamic tendency to
flow back in.
 3. When protonsdo flow back into thematrix, thefreeenergy
arising from thegradient (21 kJ/mol of protons) is dissipated,
with someof it being used to drivetheATPsynthesis.
Chemiosmotic Coupling
ATP Synthase:
ATPsynthase or F0F1 complex or
Complex V
 Head F1
 Stalk F0
P:O Ratio
 TheP:O ratio refersto:
thenumber of Inorganic Phosphatemolecules
utilized for ATPgeneration for every atom of
Oxygen (apair of e-) consumed.
.
P:O Ratio
 Electronsentering thesystem at complex I from
NADH haveaP/O ratio of about 3/1.
 Electronsentering thesystem at complex II
FADH2'shaveaP/O ratio of about 2/1.
ATP Synthesis by ATP Synthase
 Boyer’sBinding ChangeMechanism
Inhibitors of ETC
Inhibitors of ETC:
 Bind to oneof thecomponentsof ETC and Block the
transport of Electrons.
 At Complex I: Rotenone, Amytal & Piericidin A
 Between cyt b and c1: Antimycin A & BAL
 At Complex IV: CO, Cyanide, Azide& H2S
Inhibitors of Oxidative Phosphorylation:
 Uncouplers: 2,4- DNP, FCCP(trifluoro carbonyl
cyanidephenyl hydrazone)
Thyroxin, FFA
Blocksbetween oxidation and phosphorylation
 Ionophores: Valinomycin, Nigercin
altersthepermeability of mitochondrial membrane
OtherInhibitors
 Oligomycin: ATPsynthase
 Atracyloside: Adeninenucleotide
carrier(Translocase)
Thank you

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Biological oxidation ppt

  • 2.
  • 3. High energy phosphates &Low energy phosphates: Compound Phosphoenolpyruvate -14.8 Carbamoyl phosphate -12.3 1,3 – Bisphosphoglycerate -11.8 Creatine phosphate -10.3 ATP ADP + Pi -7.3 ADP AMP + Pi -6.6 Pyrophosphate -6.6 Glucose 1-phosphate -5.0 Fructose 6 –phosphate -3.8 AMP -3.4 Glucose 6 –phosphate -3.3 Glycerol 3-phosphate -2.2 Kcal/mol -7.3ATP ADP +Pi
  • 5. Importance of Adenosine Triphosphate (ATP)  ATPservesasthegeneral "freeenergy currency" for virtually all cellular processes.  It isadirect sourceof energy for cell motility, muscle contraction, and thespecific transport of substances acrossmembranes.  ATPisasourceof phosphateenergy for synthesisof the other nucleosidetriphosphatesviathereaction: ATPisalso an allosteric effector of many enzymes.
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  • 9. cytochromes: Protein-bound :- Heme containing carriers  Cytochromesconstituteafamily of colored proteinscontaining the Hemeprosthetic group
  • 10. Nature of e- Carriers: Protein-bound carriers :- Iron-sulphurcenters  Feion iscoordinated with thesulphursof cysteine residuesand inorgnic sulphur atoms.
  • 11. Nature of e- Carriers: Mobile carriers :- Coenzyme Q  CoenzymeQ: small hydrophobic moleculeand theonly onethat isnot apart of protein.
  • 12. Organization of carriers in ETC: Complex I NADH dehydrogenase complex : Largest Respiratory enzyme complex > 40 polypeptide chains Bound FMN At least 7 iron-sulfur centers Electron transfer From NADH to Co Q Blocked by Rotenone and Amytal
  • 13. Complex II SuccinateDehydrogenase: It isapoint of entry of electronsfrom FADH2 produced by theenzymesuccinatedehydrogenasein thecitric acid cycle.  FAD asProsthetic group  Iron-sulfur proteins  Electron transfer From FADH2 to Co Q  Thus, both complexesI and II donatetheir electrons to thesameacceptor, coenzymeQ.
  • 14. CoenzymeQ :  Benzoquinonelinked to 10 isopreneunits  It hastheability to accept electronsin pairsand passthem one at atimethrough asemiquinoneintermediateto Complex III. Thiscycleisreferred to astheQ cycle.  Electron transfer From Complex I or II to Complex III Cytochromec : Thissmall mobileprotein accepts e- from Complex III and shuttlesthem to Complex IV
  • 15. Complex III Cytochromeb-c1 complex : It isaDimer  Each monomer has: 3 Hemesbound to cytochromes 1 Iron-sulfur protein  Electron transfer From Co Q to cytochromec  Cytochromec then transferse- to thecomplex IV  Blocked by Antimycin A
  • 16. Complex IV Cytochromeoxidasecomplex :  Dimer  Each monomer has: 13 Different polypeptidechains, including 2 Cytochromesaand a3 and 2 Cu atoms  AcceptsoneElectron at atimefrom Cytochromec and passesthem four at atimeto Oxygen  Blocked by Cyanide, Azide, and Carbon monoxide
  • 18. Oxidative Phosphorylation  Chemical coupling  Chemiosmotic hypothesis - proposed by Mitchel - dependent on proton gradient.
  • 19.
  • 20. Chemiosmotic Coupling:  1. Theactivetransport of electronspumpsprotonsout of the mitochondrial matrix into theinter membranespace.  2. An electrochemical gradient of protonsiscreated, outsidethe inner mitochondrial membranethan inside. Theprotonson theoutsidehaveathermodynamic tendency to flow back in.  3. When protonsdo flow back into thematrix, thefreeenergy arising from thegradient (21 kJ/mol of protons) is dissipated, with someof it being used to drivetheATPsynthesis.
  • 22. ATP Synthase: ATPsynthase or F0F1 complex or Complex V  Head F1  Stalk F0
  • 23. P:O Ratio  TheP:O ratio refersto: thenumber of Inorganic Phosphatemolecules utilized for ATPgeneration for every atom of Oxygen (apair of e-) consumed. .
  • 24. P:O Ratio  Electronsentering thesystem at complex I from NADH haveaP/O ratio of about 3/1.  Electronsentering thesystem at complex II FADH2'shaveaP/O ratio of about 2/1.
  • 25. ATP Synthesis by ATP Synthase  Boyer’sBinding ChangeMechanism
  • 27. Inhibitors of ETC:  Bind to oneof thecomponentsof ETC and Block the transport of Electrons.  At Complex I: Rotenone, Amytal & Piericidin A  Between cyt b and c1: Antimycin A & BAL  At Complex IV: CO, Cyanide, Azide& H2S
  • 28. Inhibitors of Oxidative Phosphorylation:  Uncouplers: 2,4- DNP, FCCP(trifluoro carbonyl cyanidephenyl hydrazone) Thyroxin, FFA Blocksbetween oxidation and phosphorylation  Ionophores: Valinomycin, Nigercin altersthepermeability of mitochondrial membrane
  • 29. OtherInhibitors  Oligomycin: ATPsynthase  Atracyloside: Adeninenucleotide carrier(Translocase)
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