Marine eicosanoids: Occurrence of 8-(R)-HETE in the starfishPatiria miniata

Summary The first isolation of 8-(R)-hydroxy-5Z, 9E, 11Z, 14Z-eicosatetraenoic acid [8-(R)-HETE] from a marine source, the pacific starfishPatiria miniata, is reported. 8-(R)-HETE occurs together with 8-(R)-hydroxy-5Z, 9E, 11Z, 14Z, 17Z-eicosapentaenoic acid.     

Response ofHeliothis virescens to pheromonal components and an inhibitor in olfactometers

Summary Laboratory-reared males ofHeliothis virescens (F.) that were released in olfactometers in the laboratory were attracted to theH. virescens synthetic pheromone, but not to (Z)-9-tetradecen-1-ol formate (Z-9-TDF), or to either pheromonal component, (Z)-11-hexadecenal (Z-11-HDAL) or (Z)-9-tetradecenal (Z-9-TDAL). Also, they did not respond to the pheromone when it was dispersed simultaneously with Z-9-TDF. The proximity of the test chemicals in the olfactometer made little, if any, difference in the response ofH. virescens males to the pheromone source. Preexposure to the synthetic pheromone, Z-9-TDF, Z-11-HDAL, or Z-9-TDAL greatly reduced the number ofH. virescens males responding to the pheromone. This reduction was probably caused by habituation of the moths to these chemicals.The authors wish to thank A. H. Baumhover, E. Hart and other personnel of the Tobacco Research Laboratory, Oxford, N. C., for supplying many of the insects used in these studies.     

Regulatory steps in sex pheromone biosynthesis inMamestra brassicae L. (Lepidoptera: Noctuidae)

Summary The de novo biosynthesis of (Z)-11-hexadecenyl acetate, the most abundant pheromone component inM. brassicae, starting from acetate via palmitic acid, requires the presence of a pheromone-biosynthesis-activating neurohormone. Moreover, the conversion of palmitic acid to (Z)-11-hexadecenyl acetate is strongly dependent on the presence of the neurohormone. However, no significant dependence was found for the conversion of (Z)-11-hexadecenoic acid to (Z)-11-hexadecenyl acetate. This indicates that the neurohormonal control of pheromone biosynthesis inM. brassicae occurs at the level of palmitic acid.     

Chemical analysis of the pheromone blends produced by males and females of the neotropical moth,Mocis megas (Guénée) (Lepidoptera,Noctuidae, Catocalinae)

Summary Pheromonal secretions produced by females and males of the noctuid moth,Mocis megas (Guénée) have been analyzed by gas chromatography and mass spectrometry (EI (electron impact) and CI (chemical ionization)). The female sex pheromone was a blend of (Z,Z,Z) 3,6,9 heneicosatriene (55%) and (Z,Z) 3,6-cis-9S, 10R-epoxyheneicosadiene (45%). Male secretion produced at the level of a prothoracic organ was a blend of two unsaturated major hydrocarbons: (Z,Z) 6,9 heneicosadiene, (64%) and (Z,Z,Z) 3,6,9 heneicosatriene (24%) and C₁₉, C₂₀ and C₂₂ homologues (total ratio 12%), as minor components. The trienic hydrocarbon was present in both sexes. The behavioral role of this male secretion has not yet been elucidated.     

Sex pheromones of the armyworm moth,Spodoptera exempta (Wlk.

Zusammenfassung Es wurden mit gas-chromatographischer Elektroantennogramm-Methode (Z)-9-tetradecenyl-1-acetat und (Z)-9, (E)-12-tetradecadienyl-1-acetat als die Sexuallockstoffe weiblicherSpodoptera exempta (Wlk.) identifiziert.

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Acknowledgment: We are grateful to Mr.C. Rivers, Unit of Insect Virology, University of Oxford Field Station, for supplying insect pupae.     

Confirmation of sex pheromone biosynthesis from (16-D3)palmitic acid in the turnip moth using capillary gas chromatography

Summary (16-D₃)palmitic acid was applied topically to pheromone glands of the turnip moth. After incubation omega labeled analogues of fatty acid methyl esters and acetates were identified by gas chromatography with flame ionization detection and selected ion monitoring. The pheromone components (Z)-5-decenyl, (Z)-7-dodecenyl- and (Z)-9-tetradecenyl acetate were all biosynthesized from palmitic acid along a common pathway.     

A peculiar fatty acid, (Z,Z)-9,12,17-octadecatrienoic acid,identified in the phospholipids of the pea aphid,Acyrthosiphon pisum (Harris) (homoptera: aphididae)

A peculiar fatty acid previously detected in the phospholipids of the pea aphid,Acyrthosiphon pisum, is identified as (Z,Z)-9,12,17-octadecatrienoic acid. It is the first report of this compound in the literature. Comparison of fatty acid profiles of phospholipids between normal and aposymbiotic pea aphids shows that aphid symbionts are not responsible for the biosynthesis of this unusual fatty acid.     

Long-chain (Z)-9-alkenes are ‘Psychedelics’ to houseflies with regard to visually stimulated sex attraction and aggregation

Summary Three different tests on houseflies (Musca domestica L.) revealed that both pheromone-free pseudoflies and male partner flies exhibit in the presence of mixtures of long-chain (Z)-9-alkenes or pure (Z)-9-tricosene enhanced releasing effects for two optical cues, which stimulate male houseflies to mating strikes and houseflies of both sexes to aggregation.     

Bombykol biosynthesis from deuterium-labeled (Z)-11-hexadecenoic acid

Summary (Z)-[11,12d ₂]-11-Hexadecenoic acid was applied topically to the pheromone gland of silkworm pupa. After eclosion, the gland components were analyzed by capillary GC-MS. (Z)-11-Hexadecenoic acid, a characteristic fatty acid of the gland, was found to be a precursor of bombykol, (Z)-11-hexadecenol and bombyk acid.We are greatful to Dr Y. Tamaki and Mr H. Sugie of the National Institute of Agricultural Science for mass spectrometric analysis and Dr M. Noda of Kyoto Prefectural University for valuable discussion. This work was supported by a Grant-in-aid for Scientific Research (to K.H. No. 56112011) from the Ministry of Education, Science and Culture of Japan.     

Arginine-vasopressin,lysine-vasopressin,and oxytocin,C14-labeled in the glycine residue

Zusammenfassung Die Synthese von Arginin-Vasopressin, Lysin-Vasopressin und Oxytocin, deren Glycinrest eine¹⁴C-Markierung trägt, wird mit Hilfe der Festkörpermethode nachMerrifield beschrieben.

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Supported by National Institutes of Health grants No. AM-13567 and No. AM-10080 and the Atomic Energy Commission.

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Abbreviations follow the rules of the IUPAC-IUB Commission on Biochemical Nomenclature in Biochemistry5, 2485 (1966). All optically-active amino acids are ofl-configuration. The following additional abbreviations were used: N-hydroxysuccinimide ester (OSu), ethanol (EtOH), methanol (MeOH), acetic acid (AcOH),n-butanol (n-BuOH), pyridine (Pyr) and N,N-dicyclohexylcarbodiimide (DCCI). Protected peptides and hormones were visualized on thinlayer plates according to the procedure byH. Zahn andE. Rexroth, Z. analyt. Chem.148, 181 (1955). The biological activities of the hormones were measured against the U.S.P. Posterior Pituitary Reference Standard; the four-point design was used for these bioassays and standard errors were calculated according to the method ofC. I. Bliss,The Statistics of Bioassay (Academic Press, New York, N.Y. 1952).

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Acknowledgments. The authors wish to thank Mr.D. Schlesinger for some of the amino acid derivatives used, and MissM. Wahrenburg and Mrs.A. Silverman for bioassays.     

(Z)-9-tetradecen-1-ol and (Z)-9-tetradecenyl acetate: A potent attractant system for maleSesamia cretica Led. (Lep., Noctuidae)

Summary Field studies have shown that a combination of (Z)-9-tetradecenol with (Z)-9-tetradecenyl acetate is an effective attractant for maleSesamia cretica Led., a pest of sorghum crops. These studies also indicated that the most effective composition is 7525 (alcohol:acetate).We thank Dr E. Berio for the insect determination.     

Laboratory and field studies of the female sex pheromone of the olive moth,Prays oleae

Summary Analysis by GC-EAG indicates that abdominal tip extracts of femalePrays oleae contain a tetradecenal. Synthetic (Z)-7-tetradecenal elicits a strong EAG respones from maleP. oleae and field tests it to be comparable in attractancy with the virgin female moth. (Z)-9-Tetradecenal also produces a strong EAG response but it is not an attractant and, when added to (Z)-7-tetradecenal, markedly reduces trap catches.Acknowledgments. The authors are indebted to Mr N. Psylakis, Agricultural Research Centre, Chania, Crete, and to Dr D. Vassilopoulos, Benaki Phytopathological Institute, for providing facilities for this work. They thank the Commonwealth Institute of Entomology, London, for moth species confirmation.     

Acyl fluorides as reactive mimics of aldehyde pheromones: hyperactivation and aphrodisiac inHeliothis virescens

Summary Substitution of fluorine for the aldehydic hydrogen provides behaviorally active, chemically reactive pheromone mimics. In male moths of the tobacco budwormHeliothis virescens, Z9–14:Acf and Z11–16:Acf cause hyperactivity and irreversible extension of the genitalia in over 80% of treated moths. In addition, a combination of the two components leads to 10–50% of the pairs involving one treated partner becoming locked in copula.Supported by NSF grant PCM-8112755 and DMB-8316931, by a Fellowship from the Alfred P. Sloan Foundation (1981–85), and by Teacher-Scholar Grant from the Camille and Henry Dreyfus Foundation (1981–86) to G.D.P. Address correspondence to G.D.P.     

Sex attractants for maleHeliothis armigera (Hbn.)

Summary (Z)-11-Hexadecenal and (Z)-11-tetradecenal were found to be sex attractants of maleHeliothis armigera (Hbn.).This research was supported by a grant from the United States-Israel Binational Science Foundation (BSF), Jerusalem, Israel.     

Unusual antimicrobial compounds fromAeollanthus buchnerianus

Using bioassay guided isolation, three novel 12 carbon polyoxygenated fatty acids and a novel abietane diterpene have been isolated from the the chloroform extract of aerial parts ofAeollanthus buchnerianus (Lamiaceae). Rigorous spectroscopic methods were used for compound identification. (Z,Z)-8-acetoxy-5-hydroxydodeca-2,6-dienoic acid and (Z,Z)-5,8-dihydroxydodeca-2,6-dienoic acid inhibited the spore germination ofCladosporium cucumerinum (both with Minimum Inhibitory Dose (MID) values of 1 g) andAspergillus niger (MID 5 and 25 g respectively). Further, they also reduced the hyphal growth ofPythium ultimum. (Z)-5-hydroxy-6,7,8-triacetoxydodeca-2-dienoic acid exhibited short term inhibition of the growth ofCladosporium cucumerinum. The novel abietane diterpenoid, (rel)-14-acetoxyabiet-7-en-18-oic acid inhibited the growth of the gram positive bacteriaBacillus subtilis, staphylococcus aureus andStreptomyces scabies (MIC values 80, 20 and 20 g ml^–1 respectively).     

Determination of diel periodicity of sex pheromone release in three species of Lepidoptera by ‘closed-loop-stripping’

Summary By means of closed-loop-stripping and subsequent GC analyses the diel periodicity of release of (Z)-11-hexadecenyl acetate, (E)-8-dodecenyl acetate, and (Z)-9-tetradecenyl acetate, the main constituents of the respective sex pheromone blends ofMamestra brassicae, Cryptophlebia leucotreta andSpodoptera sunia females, was determined.Pheromones, 64. For the 63rd contribution we have taken from: Szöcs, G., Toth, M., Bestmann, H. J., Vostrowsky, O., Heath, R. R., and Tumlinson, J. H., Z. Naturforsch.42c (1987) 165; Pheromones, 62: Bestmann et al.¹³.     

Furan fatty acid steryl esters from the marine spongeDictyonella incisa which show inflammatory activity

Summary Three new furan fatty acids, (9Z, 19Z)-3, 6-epoxyhexacosa-3,5,19-tetraenoic acid (1a), (8Z, 11Z, 14Z, 17Z)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (2a), and (8Z, 11Z, 14Z, 17E)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (3a), and a new polyunsaturated fatty acid (5Z, 8Z, 11Z, 14Z, 17E)-eicosa-5,8,11,14,17-pentaenoic acid (6a), present in the spongeDictyonella incisa as the respective steryl esters, have been isolated as methyl esters and their structures have been determined by spectral and chemical analysis. The furan fatty acid esters have shown a high inflammatory activity, which suggests their potential role as feeding deterrents.     

An Argentine ant aggregation factor

Summary (Z)-9-Hexadecenal, a general aggregation factor of the Argentine ant,Iridomyrmex humilis, has been isolated and chemically characterized. It is implicated as a component of the trail-pheromone complex on evidence that it is a constitutent of the ventral gland secretion, and that it both activates and attractsI. humilis workers.Acknowledgments. We thank the Australian Research Grants Committee, and the Reserve Bank of Australia, Rural Credits Development Fund for financial support.     

Der Vitaminbedarf des amerikanischen ReismehlkäfersTribolium confusum Duval

Summary One component of the group of vitamines required for the normal development of the larvæ ofTribolium confusum can be fully replaced by synthetic pteroyl glutamic acid (folic acid) at a level of 0,2 per gram of diet. At least one further unknown factor contained in yeast is necessary.

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4. Mitteilung vgl.H. Rosenthal, C. A. Grob, Z. Vitaminforsch.17, 27 (1946).     

Identification of mucondialdehyde as a novel stress metabolite

In a survey of antifungal stress compounds induced by cupric chloride we found that leaves ofChenopodium album exuded a highly fungitoxic metabolite mucondialdehyde (trans-2,trans-4-hexadienedial), which was associated with 13-oxo-9,11-tridecadienoic acids (cis-9,trans-11 andtrans-9,trans-11 isomers) presumably resulting from -scission of 13-hydroperoxy-octadecadi(tri)enoic acid. The biogenesis and role as a general defensive agent in plants are briefly discussed.