Biosynthesis of 10,12-dienoic fatty acids by a bifunctional Delta11 desaturase in Spodoptera littoralis.
In the biosynthetic pathway of Spodoptera littoralis sex pheromone, (E,E)-10,12-tetradecadienoic acid is produced from (Z)-11-tetradecenoic acid by desaturation and concomitant migration of the precursor double bond. With the aim of identifying the enzyme involved in this biotransformation, yeast Deltaelo1/Deltaole mutants, which are both elongase 1 and Delta9 desaturase-deficient, were transformed with the S. littoralis Delta11 desaturase gene using a Cu+2 inducible expression vector. The transformants produced a recombinant polyhistidine-tagged Delta11 desaturase that could be detected by immunoblotting from cell lysates. Lipid analysis revealed that besides producing large quantities of C11-monounsaturated fatty acids, mainly (Z)-11-hexadecenoic acid, (E,E)-10,12-tetradecadienoic acid and minor amounts of (E,Z)-10,12-hexadecadienoic acid were also produced, as well as very low quantities of another tetradecadienoate, which was tentatively identified as the (E,Z)-10,12-tetradecadienoic isomer. None of these dienes was detected with the Delta11 desaturase gene of Trichoplusia ni, which does not produce conjugated dienes as pheromone components. We conclude that the Delta11 desaturase of S. littoralis is a bifunctional enzyme with both Delta11 and Delta10,12 desaturation activities. The relationship between the substrate structure and the stereochemical outcome of the reaction is discussed.
Serra
Montserrat
M
Department of Biological Organic Chemistry, IIQAB-CSIC, Jordi Girona 18, 08034 Barcelona, Spain.
Piña
Benjami
B
Bujons
Jordi
J
Camps
Francisco
F
Fabriàs
Gemma
G
D000818:Animals; D044943:Fatty Acid Desaturases / Q000378:metabolism*; D005229:Fatty Acids, Monounsaturated / Q000378:metabolism; D009227:Myristic Acids / Q000378:metabolism; D010169:Palmitic Acids / Q000378:metabolism; D018411:Spodoptera / Q000201:enzymology / Q000378:metabolism*
C447625:10,12-tetradecadienoic acid; C432948:11-tetradecenoic acid; D005229:Fatty Acids, Monounsaturated; D009227:Myristic Acids; D010169:Palmitic Acids; C093821:hexadecenoic acid; D044943:Fatty Acid Desaturases