CHAPTER 13
Bioenergetics and Biochemical
Reaction Types
1. bioenergetics and thermodynamics
2. chemical logic and common biochemical reactions
3. phosphoryl groups transfers and ATP
4. biological oxidation and reduction reactions
© 2008 W. H. Freeman and Company
CHAPTER 13 Bioenergetics and Biochemical Reaction Types
1. bioenergetics and thermodynamics
2. chemical logic and common biochemical reactions
3. phosphoryl group transfers
and ATP
4. biological oxidation and reduction reactions
© 2008 W. H. Freeman and Company
3. phosphoryl group
transfers and ATP
resonance forms of inorganic orthophosphate
4) Group transfer reaction-
Acyl, glycosy, and phosphoryl group
4) groups transfer
Existing one Tetrahedral
plane intermediate
Tetrahedral intermediate
Trigonal bipyramid intermediate
example of rx containing phosphate group
in kinase
phosphoryl group transfers and ATP
transition state
consumption of ATP
1. early stage of nutrient breakdown (for activation
2. interconversion of nucleoside triphosphate
3. physiological process
4. highly endergonic reactions
formation of ATP
1. substrate level phosphorylation
2. oxidative phosphorylation and photophosphorylation
3. adenylate kinase reaction
Mg+2 (or Mn+2) is a part of ATP or ADP for rxs.
A↔B
ΔGo'= +4 kcal/mol
A+ ATP ↔ B + ADP + Pi
ΔGo' = -3.3
[glutamine]
K=-------------- ~108 increase
[glutamate]
hi free E compounds
phosphorylated (or
phosphate) compounds
Superhi phosphorylated
cpds (~P)
hi phosphorylated cpds
(~P)
low phosphorylated cpds
thioesters
why hi free E? (cont'ed)
tautomerization
why hi free E?
ionization,
tautomerization (=spontaneous iosomerization by proton movement)
why hi free E?
resonance
two ways how ATP
provides Energy in
the biological
process
a.covalent coupling
b. noncovalent
coupling
(eg, myosin
movement)
Ranking of biological phosphate compounds by standard free energy of
hydrolysis
Conversion of hi energy phosphate groups among compounds
ATP ↔ ADP + Pi
ORTHOPHOSPHATE (Pi)
ATP ↔ AMP + PPi
PYROPHOSPHATE (PPi) by inorganic
pyrophosphatase to Pi
present in animal, cytosol of plant, but in plant
plastid
adenylate kinase (myo kinase)
ATP + AMP ↔ ADP + ADP
nucleoside diphosphate kinase
ATP +(d)NTP ↔ ADP +(d)NTP
CHAPTER 13 Bioenergetics and Biochemical Reaction Types
1. bioenergetics and thermodynamics
2. chemical logic and common biochemical reactions
3. phosphoryl groups transfers and ATP
4. biological oxidation and
reduction reactions
© 2008 W. H. Freeman and Company
4. Biological oxidation and reduction reactions
=oxidoreduction
= redox reaction
(oxidation) loss of e- [or O binding]
or
(reduction) gain of e- [or H binding]
dehydrogenase (2 H+ , 2e-)
oxidase ( O binding)
oxygenase (O binding from O2)
oxidation state of carbon in biomolecules
Oxidation
progression
=Emission of
energy
An oxidation reduction rx
+
oxidation reduction pair
e- donor e- acceptor
(=reductant (=oxidant
= reducing agent) =oxidizing agent)
two half rx (=two conjugated redox pair)
*reduction
eg. for organic cpd
two half rxs
oxidation state of carbon in
biosphere
electronegativity
F>O>N>Cl>Br>C=S=I>H>P
4 ways for electron transfer
1. direct transfer of electron
2. as hydrogen atoms
3. as a hydride ion ( H-)
4. direct combination with oxygen
reducing equivalent = single electron equivalent
measurement
of
the standard
reduction
potentional
(E'o)
of redox pair
electrochemical
cells
another half pair
e- flow
from lower to
higher E'o
(positive)
Nernst eq.
at 298 K
ΔG=-nF Δ E
n, number of electron transferred
F, Faraday const (23.06 kcal/Vmol)
Δ E, electomotive force (emf)=redox potential
the standard reduction potential
(E'o) ; 1M, 1 atm, 298K
ΔGo’ and ΔG at 1M for acetaldehyde & NADH, 0.1 M for ethanol & NAD+
universal electron carriers in metabolism
(water soluble) NAD (P)-ligand
FMN, FAD -usually prosthetic group of
flavoproteins
(lipid soluble) ubiquinone
plastoquinone
iron-sulfur proteins
cytochromes
