Chemo-Enzymatic Synthesis of Optically Active γ- and δ-Decalactones and Their Effect on Aphid Probing, Feeding and Settling Behavior

• Published in: PloS one Vol. 11; no. 1; p. e0146160
• Main Authors: Boratyński, Filip, Dancewicz, Katarzyna, Paprocka, Marlena, Gabryś, Beata, Wawrzeńczyk, Czesław
• Format: Journal Article
• Language: English
• Published: United States Public Library of Science 2016; Public Library of Science (PLoS)
• Subjects: Alcohol; Alcohol dehydrogenase; Alcohol Dehydrogenase - genetics; Alcohol Dehydrogenase - metabolism; Alcohols; Animals; Antimicrobial agents; Aphidoidea; Aphids - drug effects; Aphids - physiology; Biology; Biotransformation; Brassica - parasitology; Chemistry; Chromatography; Decalactone; Diols; E coli; Ecology; Elater ferrugineus; Enantiomers; Enzymatic synthesis; Enzymes; Erethizon dorsatum; Escherichia coli - genetics; Escherichia coli - metabolism; Feeding; Feeding behavior; Feeding Behavior - drug effects; Feeding Behavior - physiology; Food; Gene Expression; Horses; Insect Repellents - chemical synthesis; Insect Repellents - metabolism; Insect Repellents - pharmacology; Insects; Isomers; Lactones; Lactones - chemical synthesis; Lactones - metabolism; Lactones - pharmacology; Life sciences; Liver; Myzus persicae; Optical activity; Optical Rotation; Osmoderma eremita; Oxidation; Pachycondyla apicalis; Pheromones; Phloem - parasitology; Recombinant Proteins - genetics; Recombinant Proteins - metabolism; Settling; Settling behavior; Stereoisomerism; Whiskey; Poland
• ISSN: 1932-6203; 1932-6203
• DOI: 10.1371/journal.pone.0146160

The enantiomerically enriched γ- and δ-decalactones (4a and 4b) were prepared from corresponding racemic primary-secondary 1,4- and 1,5-diols (1a and 1b), as products of enzymatic oxidation catalyzed by different alcohol dehydrogenases. The results of biotransformations indicated that the oxidation processes catalyzed by alcohol dehydrogenase (HLADH), both isolated from horse liver and recombinant in Escherichia coli, were characterized by the highest degree of conversion with moderate enantioselectivity of the reaction. Useful, environmentally friendly extraction procedure of decalactones (4a and 4b) based on hydrodistillation using a Deryng apparatus was developed. Both racemic lactones (4a and 4b), as well as their enantiomerically enriched isomers, were tested for feeding deterrent activity against Myzus persicae. The effect of these compounds on probing, feeding and settling behavior of M. persicae was studied in vivo. The deterrent activity of decalactones (4a and 4b) against aphids depended on the size of the lactone ring and the enantiomeric purity of the compounds. δ-Decalactone (4b) appeared inactive against M. persicae while γ-decalactone (4a) restrained aphid probing at ingestional phase. Only (-)-(S)-γ-decalactone (4a) had strong and durable (i.e. lasting for at least 24 hours) limiting effect, expressed at phloem level.