Structure and Biosynthesis Mechanism of Rubber from Fungi

Abstract

Abstract The structure of both terminal units and alignment of the isoprene units give conclusive evidence for the initiation and termination mechanisms of rubber formation in fungi. As shown in Figure 4, the polymerization is estimated to start from trans, trans-farnesyl pyrophosphate and proceeds by successive condensation of IPP to form isoprene units in the cis configuration. The termination is presumed to occur by direct esterification of polyisoprenyl pyrophosphate (PIP-PP) or dephosphorylation of PIP-PP followed by esterification with fatty acids. It is remarkable that the hydroxyl terminal group corresponding to the saponification product from the esterified terminal group was observed in the rubber samples by extraction from sporophores of L. volemus after storage for 2–3 days in a refrigerator without the addition of salt. In these samples, unidentified 13C-NMR signals were also detected. These findings suggest that the direct esterification of PIP-PP is more likely as a termination reaction. It also suggests the occurrence of a chemical or biochemical modification of both terminal groups and the main chain during storage. This is the first information on the termination mechanism of controlling the molecular weight of natural rubber.