Metabolic Biochemistry – BIBC102

Lecture 8

October 14, 2013

Nicotinamide-Adenine Dinucleotide

NAD
- one of the most common co-factors in
biochemical redox reactions
 transfer of hydride ion

(two electrons, one proton)

in one step
 A = e x c x l
= extinction coeff. X conc. X pathlength
LNC Fig. 13.15b (see Chapter 3, p. 76 for more on Beer’s Law)
Other important electron acceptors
• FAD – flavin adenine dinucleotide

• FMN – flavin mononucleotide

 +
FMN
+
FAD

two steps

one electron and one proton

transferred in each step

GLYCOLYSIS

Fermentation

Chapter 14 in Lehninger
The famous philosopher Ernest Renan said of Pasteur's method of research,

"This marvelous experimental method eliminates certain facts, brings forth

others, interrogates nature, compels it to reply and stops only when the mind is
fully satisfied. The charm of our studies, the enchantment of science, is that,
everywhere and always, we can give the justification of our principles and the
proof of our discoveries."
Note the formal way to represent stereo isomers of hexoses (aldose); see p. 237.
No need to memorize all of them.
Linear structures are in
equilibrium with circular structures

Cyclization yields two isomers,

 and 
GLYCOLYSIS

Fermentation

Chapter 14 in Lehninger
Glu + ATP  Glu 6-P + ADP a group transfer reaction
Glu 6-P  Fru 6-P an isomerization
Fru 6-P + ATP  Fru 1,6-bisphosphate a group transfer
 after ring opening:

CH20~P
CH20~P CH20~P

C O
C O C O

HOC H
HO C H HOC H
- H
+
H C O H HC O H
HC O

H C OH HC OH
HC OH

CH2O~P CH2O~P
CH2O~P
Fru 1,6-bisphosphate
 formation of a
Schiff base
as a
covalent intermediate
in the aldolase
reaction
 Schiff Base Formation

R R

primary amine
aldehyde or ketone C=O H2 N - C

H H
H2 O
H 2O

R R
+
protonated Schiff Base C= N C
:

H
H H
Breakage of a C – C bond facilitated by formation of a covalent intermediate
(protonated Schiff base) with the enzyme
DHAP  GAP an isomerization
 DHAP

Fru-1,6-bisP

GAP
a mixed anhydride
a high energy phosphate
Formation of a thioester intermediate in the

GAP dehydrogenase reaction

a thioester intermediate
a thioester intermediate
1,3-bisPG + ADP

3-PG + ATP
End of Lecture 8

October 14, 2013