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Pentose Phosphate Pathway

Gateway to Ribose and NADPH

The pentose phosphate (PP) pathway serves a number of functions.


As the name implies, pentose biosynthesis is through this pathway. Ribose,
ribulose, xylulose, are typical 5-carbon sugars made in the pathway. Because
pathway reactions lead to fructose-6-PO4 and glyceraldehyde-3-PO4 in a
round about way, early workers considered its only function was to backup
glycolysis. The PP pathway, however, is a major producer of NADPH for the
synthesis of fatty acids, which you will study later. Look for two unique
enzymes transketolase and transaldolase in the PP pathway. It is certainly
not a ho-hum pathway and to consider PP a backup to glycolysis is
demeaning.
The hexose phase of the pathway starts with glucose-6-PO4 (click 1). Focus on the carbonyl
group (C-1) for the next step (click 1). The first reaction is an oxidation of C-1catalyzed by the enzyme
glucose-6-PO4 dehydrogenase (click 1). The product 6-phosphoglucono--lactone is an internal ester, not
a hemiacetal. Note that C-1 is oxidized to a COOH group (click 1) You would expect NAD+ to be the
oxidizing coenzyme, but the cell has other surprises in mind. NADP + is used instead (click 1). The
product NADPH is a very important coenzyme for biosynthetic reactions. An internal ester of a sugar is
called a lactone. Remember this, because you want to remember the name of the first intermediate and
the next reaction in the pathway. In the next reaction the lactone ring is opened by the enzyme lactonase
(click 1). The final hexose product is a sugar acid, 6-phosphogluconate. These are the 3 reactions of the
hexose phase of the pathway . Note the major event was to oxidize the sugar with the phosphate group
staying on the molecule. You did not see this in glycolysis. Click 1 to go on.
COO-
CH2OPO3= NADP+ NADPH CH2OPO3= H-C-OH
O O
OH HO-C-H
OH Glucose-6-PO4
OH =O
HO dehydrogenase HO Lactonase H-C-OH
OH OH H-C-OH
Glucose-6-PO4 6-phosphoglucono--lactone
CH2 OPO3=
Hexose Phase 6-phosphogluconate
The second phase is catalyzed by one enzyme, 6-phosphogluconate dehydrogenase. The
sugars ribulose-5-PO4 (Ru5P) is the first 5-C sugar to appear (click 1). To make this sugar, a carbon as
CO2 must be removed (click 1). The CO2 comes from a COOH group. This is why it was necessary to
oxidize C-1 of glucose-6-PO4. Recall, that when a COOH group is removed the electron pair stays with
the source molecule (click 1). The electron pair attracts a proton to form a CH2OH on the new C-1 (click
1). In the final reaction a hydride ion (red) is abstracted from C-2 leaving a carbonium ion on C-2. That
reaction requires a NADP+ and in the process a second NADPH is formed in the pathway. The final step
is to rearrange electrons on C-2 to give the product ribulose-5-PO4 . Note that there are two intermediate
forms that remain bound to the enzyme (click 1). Click 1 to go on.

6-phosphogluconate dehydrogenase
COO- H
H
H-C-OH H-C-OH H-C-OH CH2OH

HO-C-H CO2 HO-C-H NADP+ NADPH HO-C + C=O

H-C-OH H-C-OH H-C-OH H-C-OH


H-C-OH H-C-OH H-C-OH H-C-OH
CH2 OPO3= CH2 OPO3= CH2 OPO3= CH2 OPO3=

6-phosphogluconate Ribulose-5-PO4
[Enzyme-bound intermediates]
Having made the ribulose-5-PO4 (click 1), its a simple matter to make the other 5-C sugars in
the pathway. This is accomplished by two enzymes, an isomerase and a epimerase. The epimerase changes
the stereochemistry of C-3 (click 1). The isomerase interchanges the keto-aldo groups (click 1). The result
is two new pentoses, ribose-5-PO4 and xylulose-5-PO4 (click 1). These are to two sugars that will take part
in the next series of reactions. Click 1 to go on.

CH2OH
Ribulose-5-PO4 C=O
H-C-OH
H-C-OH
CH2OP
Ribulose-5-PO4
Epimerase Ribulose-5-PO4
Isomerase

CH2OH CHO
C=O H-C-OH
HO-C-H H-C-OH
H-C-OH H-C-OH
Xylulose-5-PO4 Ribose-5-PO4
CH2OP CH2OP
The last phase of this most interesting pathway involves two special enzymes, a transketolase and a
transaldolase. The transketolase starts the pathway by condensing ribose-5-PO4 with xylulose-5-PO4 (click 1).
In the reaction the keto group of the xylulose-5-PO4 (first 2 carbons) is transferred to the receiving ribose-5-
PO4(click1) This results in the formation of a 7 carbon intermediate, sedoheptulose-7-PO4 (S7P) leaving behind
3 carbons that rearrange to form glyceraldehyde-3-PO4 (GAP) (click 1). The GAP reacts with S7P in a reaction
catalyzed by transaldolase to form a 6-carbon fructose-6-PO4, leaving behind erythrose-4-PO4 (E4P) (click 1).
E4P condenses with a second xylulose-5-PO4 to give a second molecule of F6P and GAP (click 1). That last
reaction is catalyzed by a transketolase.
CH2OH
Transketolase CH2OH Transaldolase C=O
C=O HO-C-H Fructose-
CH2OH CHO
HO-C-H H-C-OH 6-PO4
C=O
+ H-C-OH H-C-OH
HO-C-H H-C-OH CHO CH2OP
H-C-OH H-C-OH H-C-OH Trans-
CH2OP CH2OP H-C-OH ketolase
Xylulose-5-PO4
CH2OP
Ribose-5-PO4
Sedoheptulose-7-PO4
Erythrose-4-PO4 CH2OH
C=O
CHO HO-C-H
H-C-OH H-C-OH
CH2OP CH2OP
Glyceraldehyde-3-PO4
Xylulose-5-PO4
What you have learned. Click 1 for answers.

1. How many ATPs are produced by the oxidation of 1 glucose molecule in the pentose
phosphate pathway?
None. The pathway is not designed to produce ATP

2. How many ATPs are required to produce the final products of the pathway?
None. The pathway does not require ATP

3. How many NADPHs are produced by oxidation of 3 glucose molecules in the pentose
phosphate pathway?
Six. Two for each glucose oxidized.
4. Is the pentose phosphate pathway considered anaerobic or aerobic? Anabolic or
catabolic? Explain.
Anaerobic and Anabolic. The pathway does not require oxygen. Therefore, it is an
anaerobic pathway. Since it results in the synthesis of pentoses and NADPH, it must be
considered primarily anabolic.