Chemical defense in the three European species ofCrematogaster ants

The composition of the Dufour gland of the antC. scutellaris has been reinvestigated by gas chromatography/mass spectrometry. The major components of the gland are (2E,5E,12Z)-4-oxoheneicosa-2,5,12-trien-1-ol acetate (1a) its ¹⁴ and ¹⁶ double bond isomers (1b and1c), and the corresponding (Z,Z)-dienes5a and5b, all containing an acetylated C₂₁ chain. The previously proposed structures1d, 1e, and5c, which are based on an homologous acetylated C₂₃ chain, correspond to minor derivatives present in the gland. Traces of acetylated C₁₉ homologs, tentatively identified as1g-1i, have also been found. The Dufour gland contents of the two other EuropeanCrematogaster species have also been studied.C. auberti is very similar toC. scutellaris in producing mainly1a, 1b and1c, together with the same higher and lower homologs, but it lacks the dienic derivatives5, whereasC. sordidula contains essentially the acetylated C₁₉ compounds1g, 1h, and1i, accompanied by acetylated C₁₇ homologs.     

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.     

A potent actomyosin ATPase activator from the Okinawan marine spongeAgelas cf.nemoechinata

Summary A bromine-containing alkaloid, oxysceptrin, has been isolated as a potent actomyosin ATPase activator from the Okinawan marine spongeAgelas cf.nemoechinata, and the structure elucidated to be1 on the basis of the 2D NMR spectral data.Acknowledgments. We thank Mr Z. Nagahama for his help in sponge collecting and Ms M. Takamatsu for her technical assistance.     

A potent attractant of zoospores ofAphanomyces cochlioides isolated from its host,Spinacia oleracea

A highly potent attractant of zoospores ofAphanomyces cochlioides, a causal fungus of the root rot disease of spinach (Spinacia oleracea), was isolated from spinach roots, and its structure was determined by spectroscopic evidence and chemical synthesis as cochliophilin A (5-hydroxy-6,7-methylenedioxyflavone,1). A chromosorb particle prepared by soaking in solution of1 showed a potent attracting activity toward the zoospores using concentrations of1 above 10^–9 or 10^–10 M.     

Desacetylscalaradial,a cytotoxic metabolite from the spongeCacospongia scalaris

Summary From the marine spongeCacospongia scalaris, scalaradial1, desacetylscalaradial2, and heteronemin3 were isolated. Compound2 showed potent cell growth inhibition. The stereochemistry of3 is briefly discussed.Acknowledgments. The authors are grateful to Prof. T. Hase and Mr R. Nakai for collecting the sponge and to Dr s. Tanida for the sponge identification.     

Luffariellolide,an anti-inflammatory sesterterpene from the marine spongeLuffariella sp.

Summary Luffariellolide (2) is a sesterterpene from the Palauan spongeLuffariella sp. that has useful anti-inflammatory properties. In contrast with the irreversible action of manoalide (1) on phospholipase A₂, luffariellolide (2) is a slightly less potent but partially reversible PLA₂ inhibitor.30 December 1986Acknowledgment We thank Edward Luedtke, Elise Clason and Ellen Snideman for performing some of the assays reported above. The sponge was identified by Dr. Klaus Rützler, Smithsonian Institution, Washington, D.C. The research was supported by grants from Allergan Pharmaceuticals and the California Sea Grant College Program (Projects R/MP-30 and R/MP-31).     

Alarm pheromones from the Mediterranean opisthobranchHaminoea navicula

Summary Structure and absolute stereochemistry of two new 3-alkylpyridines, haminol-A (3) and haminol-B (4), isolated from the cephalaspidean molluscHaminoea navicula, have been determined by means of spectral and chemical methods. Haminols are secreted byH. navicula when it is molested, and these induce an alarm response in trail-following conspecifics.In part presented at the 32nd IUPAC Congress Stockholm, 2–7 August 1989. Cimino, G., and Sodano, G., Abstracts SL 302, p. 63.     

A non-peroxide norsesterterpene from a marine spongeHyrtios erecta

Summary A new norsesterterpene, hyrtial4, and known sesterterpenes,1–3, have been isolated from an anti-inflammatory active crude extract of the spongeHyrtios erecta.This sponge,Hyrtios (Heteronema) erecta Keller 1889, collected in 1980/81, from Tonga was extremely abundant in the Vava'u Is. Group.We thank Prof. R. Jacobs and his research group at UCSB for this data.     

Biomedicine and diseases: the Klippel-Trenaunay syndrome, vascular anomalies and vascular morphogenesis

Vascular morphogenesis is a vital process for embryonic development, normal physiologic conditions (e.g. wound healing) and pathological processes (e.g. atherosclerosis, cancer). Genetic studies of vascular anomalies have led to identification of critical genes involved in vascular morphogenesis. A susceptibility gene, VG5Q (formally named AGGF1), was cloned for Klippel-Trenaunay syndrome (KTS). AGGF1 encodes a potent angiogenic factor, and KTS-associated mutations enhance angiogenic activity of AGGF1, defining ‘increased angiogenesis’ as one molecular mechanism for the pathogenesis of KTS. Similar studies have identified other genes involved in vascular anomalies as important genes for vascular morphogenesis, including TIE2, VEGFR-3, RASA1, KRIT1, MGC4607, PDCD10, glomulin, FOXC2, NEMO, SOX18, ENG, ACVRLK1, MADH4, NDP, TIMP3, Notch3, COL3A1 and PTEN. Future studies of vascular anomaly genes will provide insights into the molecular mechanisms for vascular morphogenesis, and may lead to the development of therapeutic strategies for treating these and other angiogenesis-related diseases, including coronary artery disease and cancer.Received 24 November 2004; received after revision 21 January 2005; accepted 2 March 2005     

6H-anthra[1,9-bc]thiophene derivatives from a bryozoan,Dakaira subovoidea

Separation of a lipophilic extract of the bryozoan,Dakaira subovoidea, a common fouling organism of underwater structures, guided by inhibition of lipid peroxide formation in rat liver microsomes, gave 5,7-dihydroxy-1-hydroxymethyl-6-oxo-6H-anthra[1,9-bc]thiophene (1a) and its 1-methoxycarbonyl derivative (1c), together with the known 1,8-dihydroxyanthraquinone (2). The structures were determined by spectral and crystallographic analyses.     

Structure assignments of two new C-18-oxygenated steroidal ketals isolated from a pacific soft coral of the genusSinularia

Summary Two new C-18-oxygenated sterols possessing a spiroketal function (1 and2) have been isolated from a soft coral of the genusSinularia. The proposed structures are based on spectral data.     

Cardenolide glycosides from the adults and eggs ofChrysolina fuliginosa (Coleoptera: Chrysomelidae)

Besides the known sarmentogenin 3-O--D-allopyranoside (1) and digitoxigenin-3-O-[-D-xylopyranosyl-(14)-2, 3-di-O-acetyl--D-allopyranoside] (4), four new cardiac glycosides (2, 3, 5 and6) have been isolated from the defensive glands of adults ofChrysolina fuliginosa. The structures of the new compounds were determined by¹H NMR at 600 MHz and FABMS. Compounds1–6, present in the adults ofC. fuliginosa, have also been identified in the eggs.     

Guggulsterol-like steroids from the Mediterranean gorgonianLeptogorgia sarmentosa

Summary Several polyoxygenated steroids (1, 2, 3) have been isolated from the marine gorgonianLeptogorgia sarmentosa. One of these (1) is the known guggulsterol III, previously found in the pharmacologically active resin from the treeCommiphora mukul; the others,2 and3, have not been found before in nature, and are closely related to1. During the structural work apparent anomalies in the CMR-spectra of1 were observed.The authors are grateful to Prof. Sukh Dev for the PMR-spectra of guggulsterol III. Thanks are also due to Zoological Station (Naples), for the collection of the gorgonian, to Centro Metodologie Chimico-Fisiche, Università di Napoli, for recording PMR-spectra on WH-270 Superconducting Spectrometer-Bruker, to Mr C. Di Pinto for the CMR-spectra and to Mr A. Milone for the MS spectral measurements.     

Relative phase difference as an index of the quantity of the secretory material in the neurosecretory cell ofIphita limbata

Zusammenfassung Die sogenannte Phasenverzögerung in neurosekretorischen Zellen beim weiblichen KäferIphita limbata vor und nach der Eiabsonderung ist verschieden und wird als Index für die Quantität der neurosekretorischen Substanz betrachtet.     

Structure of victorin C,the major host-selective toxin fromCochliobolus victoriae

Summary The predominant host-selective toxin fromCochliobolus victoriae, victorin C, is a peptide with an apparent mol. wt of 796, representing a cyclic array of the subunits1–6. The structure of the toxin has now been established as in16 through analysis of the degradation products generated by enzymic and non-enzymic partial hydrolysis. The presence of a hydrated aldehydo group requires for victorin C the composition C₃₁H₄₅O₁₃N₆Cl₃ with an amended mol. wt of 814, for which independent experimental support has been secured.     

New aromatic esters of the liverwort,Trichocolea tomentella

Summary 4 new aromatic esters containing isoprene units have been isolated from the liverwort,Trichocolea tomentella, and their structures have been established to be1, 2, 3 and4.The authors are indebted to Professor G. Ourisson of Université Louis Pasteur de Strasbourg, France, and Dr S. Hattori of the Hattori Botanical Laboratory for their helpful suggestion to this work.     

The site of synthesis of hemocyanin in the crayfish,Astacus leptodactylus

Summary The in vitro incorporation of³⁵S-methionine into hemocyanin was tested in the crayfish,Astacus leptodactylus. All organs assayed (hemocytes, heart, hypodermis, midgut gland, muscle and stomach) were able to synthesize proteins under our experimental conditions, but only midgut gland (=hepatopancreas) incorporated labeled methionine into a protein which was precipitated by an antibody againstAstacus hemocyanin, and which comigrated with authentic hemocyanin on SDS gels.     

Characterization of 17β-estradiol 3-(β-D-glucopyranoside) and 17-(α-D-glucopyranoside) as the metabolites of 17β-estradiol in the cultured ovaries of the silkworm,Bombyx mori

Summary The structures of the metabolites formed upon incubation of 17-estradiol with the ovaries of silkworm,Bombyx mori, have been determined as 17-estradiol 3-(-D-glucopyranoside) (1) and 17-(-D-glucopyranoside) (2) by spectroscopic means.     

Zur Stereochemie der Propandioldehydrase-Reaktion

Summary Propanedioldehydrase is shown to convert both (+)-(S)-2-²H-propanediol,3, and (–)-(R)-1-²H₂-propanediol,5, to specimens of deuterated propion-aldehyde, for which the (S)-configuration has been established. Thus, in the propanedioldehydrase reaction migration of hydrogen atoms from C–1 to C–2 always occurs with inversion of configuration.     

A new 9,11-secosterol,stellettasterol from a marine spongeStelletta sp

A new 9,11-secosteroid, stellettasterol (1) was isolated from a Japanese marine sponge,Stelletta sp.; its structure was determined by spectroscopic analysis. All NMR signals of1 were unambiguously assigned by application of various 2D NMR techniques. Stellettasterol exhibited antifungal activity againstMortieralla ramannianus.Part 62 of the Bioactive Marine Metabolites series. Part 61: Fusetani, N., Takahashi, M., and Matsunaga, S., Tetrahedron, in press.