PEP carboxylase :
In C4 pathway, PEP carboxylase is the primary enzyme that fixes the atmospheric CO2 in the mesophyll cells.
CO2 in the form of HCO3- reacts with phosphoenol pyruvate (PEP) and forms Oxaloacetate (OAA), a four-carbon product. This reaction is catalyzed by PEP carboxylase.
RubisCO :
OAA formed in the mesophyll cells is converted to malic acid and is transferred to the bundle sheath. The malic acid produces carbon dioxide and pyruvate. Carbon dioxide further enters the Calvin cycle. RubisCo is the primary enzyme that catalyzes the reaction that fixes carbon dioxide and forms PGA in the Calvin cycle.
In the C4 pathway the Calvin cycle occurs in the bundle sheath cells as the enzyme RubisCo is present in the bundle sheath cells.