Biological oxidation

The ATP Cycle

High energy bonds

Phosphoanhydrite – large negative ΔG of hydrolysis, high energy bonds represented by “~”.
Phosphocreatine (creatine phosphate) – must know structure. Used for storage of ~P bonds.
Catalyzes reaction: creatinephosphate + ADP <--> ATP + creatine.
Phosphoenolpyruvate (PEP) – converts ester to ketone
Other example for phosphate esters: linkage between glucose-6-phosphate

A thioester formes between a carboxylic acid and a thiol (SH), e.g, the thiol of coenzyme A.
Thiol of coenzyme A can react with carboxyl group of acetic acid – acetyl-CoA.

Coenzyme A contains ADP – 3' – phosphate. Pantothenate. Functional group – thiol group β-
mercaptoethylamine.

Roles:

• energy transfer and storage: ATP, PPi ,polyphosphate, creatinephosphate

• Group transfer: ATP, coenzyme A
• Transient signal: cAMP

Oxidation and reduction:

In organic chem = dehydrogenation.

Catababolism is oxidative
Anabolism is reductive

NAD+
Nicotinamide adenine dinucleotide
nicotinamide ring accepts 2 e and H+ and goes to reduced state (Must know structures).

FAD
Flavin adenine dinucleotide

ATP can form on the substrate level (direct) and by oxidative phosphorelation.

Respiratory Chain

• Electron transport: carried by reduced coenzyme

• Oxidative phosphorelation
• At inner mitochondrial membrane

Electron transport
• Four protein complexes
• coenzymes + shuttle
Must know: complexes + coordinating product.

ATP contains: F1 part (α3, β3, γδε), F0 part

Important: what is the P/O ratio?

Inhibitors of oxidative phosphorylation

rotenone inhibits complex-1
cyanide, azide and CO inhibits complex 4
oligomycin inhibit ATP synthesis.