PENTOSE PHOSPHATE PATHWAY

CARBON METABOLISM IN CHLOROPLASTS

PENTOSE PHOSPHATE PATHWAY
(REDUCTIVE)
The reductive pentose phosphate cycle (RPP cycle) or photosynthetic carbon reduction cycle
is the basic biochemical pathway whereby carbon dioxide is converted to sugar phosphates in
the stroma of the chloroplast during the process of photosynthesis. This pathway is apparently
ubiquitous in all photoautotrophic green plants. In some higher plants, commonly designated
C4 plants, there is an additional pathway (C4 cycle) via which carbon dioxide is first
incorporated into four-carbon acids or amino acids and is later released to be refixed via the
RPP cycle. However, the C4 cycle is not an alternative to the RPP cycle. It does not result in
any net reduction of CO2. Its function appears to be to bring carbon into the chloroplasts
where the RPP cycle is operating. By this process, C 4 plants maintain a higher level of CO2 at
the local environment of the carboxylation enzyme of the RPP cycle, ribulose 1,5-
bisphosphate carboxylase oxygenase (RUBISCO). The result is to diminish the oxygenase
activity of this enzyme which can convert the carboxylation substrate, ribulose 1,5-
bisphosphate (RuBP) to glycolate, a substrate for the apparently wasteful process of
photorespiration.
The equation for the overall RPP reaction is:

The overall reaction pathway is cyclic and is also called Calvin cycle after the scientist who
first investigated it, Melvin Calvin, winner of the 1961 Nobel Prize in chemistry.

The Calvin cycle comprises three stages:

1. Fixation of CO2 by ribulose l, 5-bisphosphate to form two molecules of 3-
phosphoglycerate catalyzed by the enzyme ribulose-1,5-bisphosphate
carboxylase/oxygenase (rubisco). This enzyme is one of the most abundant proteins in
nature, as it accounts for about 15% of the total protein in chloroplasts.
2. Reduction of 3-phosphoglycerate to form hexose sugars
3. Regeneration of ribulose 1,5-bisphosphate so that more CO2 can be fixed.
The six carbon residues (2 molecules of glyceraldehyde-3-P) salvaged in the Calvin cycle can
either be used for the organic compounds synthesis (aromatic amino acids, phenylpropanoids,
starch) in the stroma of the chloroplast or be transported to the cytosol where they can used
for the synthesis of amino acids, sucrose, cellulose, etc.

PENTOSE PHOSPHATE PATHWAY

(OXIDATIVE)
The pentose phosphate pathway (also called as the hexose monophosphate pathway or 6-
phosphogluconate pathway) occurs in the cytosol of the cell and meets the need of all
organisms for a source of NADPH to use in reductive biosynthesis. Almost 10-25 % of the
glucose is metabolized through this pathway. This pathway consists of two phases:
1. Oxidative generation of NADPH
2. Non-oxidative interconversion of sugars
In the pentose phosphate pathway, the production of ATP is not the crux of the matter. As the
name of the pathway indicates, five-carbon sugars, including ribose, are produced from
glucose. Another important facet is the production of nicotinamide adenine dinucleotide
phosphate (NADPH), a compound that differs from nicotinamide adenine dinucleotide
(NADH) by having one extra phosphate group esterified to the ribose ring of the adenine
nucleotide portion of the molecule. A more important difference is the way these two
coenzymes function. NADH is produced in the oxidative reactions that give rise to ATP.
NADPH is a reducing agent in biosynthesis, which, by its very nature, is a reductive process.
Oxidative reactions of the pentose phosphate pathway
The oxidative portion of the pentose phosphate pathway consists of three reactions that lead
to the formation of ribulose-5-phosphate, CO2 and two molecules of NADPH for each
molecule of glucose 6-phosphate oxidized. The pentose phosphate pathway may account for
between 15 and 30% of the hexose phosphate oxidised to glyceraldehyde 3-P and CO 2. In the
first reaction of the pathway, glucose-6-phosphate is oxidized to 6- phosphogluconate. The
enzyme that catalyzes this reaction is glucose-6-phosphate dehydrogenase. NADPH is
produced by the reaction. The next reaction is an oxidative decarboxylation, and NADPH is
produced once again. The 6-phosphogluconate molecule loses its carboxyl group, which is
released as carbon dioxide, and the five-carbon keto-sugar ribulose-5-phosphate is the other
product. The enzyme that catalyzes this reaction is 6-phosphogluconate dehydrogenase.

Non-oxidative reactions of the pentose phosphate pathway

The nonoxidative reactions of the pentose phosphate pathway produce five-carbon sugars,
particularly ribose. They are important when an organism has less need for NADPH but
needs the sugars.
There are two different reactions in which ribulose-5-phosphate isomerizes. In one of these
reactions, catalyzed by phosphopentose-3-epimerase, there is an inversion of configuration
around carbon atom 3, producing xylulose-5- phosphate, which is also a ketose. The other
isomerization reaction, catalyzed by phosphopentose isomerase, produces a sugar with an
aldehyde group (an aldose) rather than a ketone. In the second reaction, ribulose-5-phosphate
isomerizes to ribose-5-phosphate. Ribose-5-phosphate is a necessary building block for the
synthesis of nucleic acids and coenzymes such as NADH. The products of these non-
oxidative reactions include substances such as fructose-6-phosphate and glyceraldehyde-3-
phosphate, which play a role in glycolysis.

In the pentose phosphate pathway, glucose-6-phosphate can be converted to fructose-6-

phosphate and glyceraldehyde-3-phosphate by a means other than the glycolytic pathway. For
this reason, the pentose phosphate pathway is also called the hexose monophosphate shunt.