Callyspongynes A and B: New polyacetylenic lipids from a southern australian marine sponge, Callyspongia sp

Abstract

A Callyspongia sp. collected by SCUBA off Barwon Heads, Australia, has afforded two new polyacetylenic lipids, callyspongynes A and B, the structures of which were assigned by spectroscopic analysis and chemical derivatization. Lipids 33, 639-642 (1998).Polyacetylenic lipids represent a class of natural product common to marine sponges, with many examples reported in recent years of this structure class varying in chain length, degrees of unsaturation, and biological activity (antimicrobial, antitumor, antifungal, and antiviral). Sponge genera known to feature polyacetylenic lipids include Petrosia (1-8), Cribrochalina (9-12), Tetrosia (13), Xestospongia (14,15), Siphonochalina (16), Reniera (17), Haliclona (18), and Callyspongia (19). This latter observation together with our recent experience in isolating novel lipids from a southern Australian Callyspongia sp. (20) prompted an investigation of the lipid content of another Callyspongia sp. in our collection. This report describes the results of a chemical analysis of a Callyspongia sp. collected by SCUBA at ~30 m depth off Barwon Heads (Victoria, Australia). EXPERIMENTAL PROCEDURESAll solvents were redistilled before use. Rapid silica filtrations were carried out using Kieselgel 60 silica gel loaded into a sintered glass funnel and eluted under low vacuum. Solid phase extraction was carried out using Alltech Maxiclean silica 900 mg cartridges (Alltech Corp., Deerfield, IL) attached to luer lock syringes. High-performance liquid chromatography (HPLC) was performed on an ISCO 2350 solvent delivery system (ISCO Corp., Lincoln, NE) equipped with a rheodyne injector, Waters 401 differential refractometer and Spectra Physics 200 programmable UV/VIS wavelength detector, and recorded on either Chart V3.2 data collection package using an AD Instruments Mac Lab/2E operating on an Apple Macintosh LC; or a Data Acquisition Plotting and Analysis (DAPA) package operating on an Ipex 286PC unit under DOS 5.0. Thin-layer chromatography was carried out on Machery-Nagel Duren Alugram Sil G/UV 254 plates and visualized by both short (254 nm)-and long (365 nm)-wavelength ultraviolet light, as well as spraying with 5% vanillin in H 2 SO 4 /H 2 O (50% wt/vol) and heating at 100°C for 2-5 min. Chiroptical measurements [α] D were obtained on a Jasco DIP-1000 digital polarimeter in a 100 mm × 2 mm cell. Infrared (IR) spectra were acquired on a Perkin-Elmer 1600 Fourier transform IR spectrophotometer. Nuclear magnetic resonance (NMR) experiments were performed on either a Varian Inova 400, Varian Unity 300, or a Varian Unity plus 400 spectrometer in the solvents indicated, with 1 H NMR referenced to residual solvent resonances and 13 C NMR to carbon resonances.Electrospray ionization (ESI) (1:1 acetonitrile/water matrix) mass spectra were acquired on a Micromass Quattro II mass spectrometer at the cone voltages indicated. Electron impact ionization (EI) (70 eV) mass spectra were acquired on a JEOL ax-505H mass spectrometer. High-resolution ESI (1:1 acetonitrile/water matrix) mass measure...

Biosynthesis and function of polyacetylenes and allied natural products

“…44). Callyspongynes A and B (40A-B), as major (C 33 ) and minor (C 35 ) components, were purified from Australian sponges and found to have an absolute configuration of (3R) [397]. Callypentayne (40C), callyberyne B (40D), and callytetrayne (40E) are simple hydrocarbons, which is unusual for marine polyacetylenes [398,399].…”

Identification of Novel Acetylenic Alcohols and a New Dihydrothiopyranone from the Tropical Sponge Reniochalina sp.

“…Acetylenic alcohols, a group of sponge metabolites, exhibit great structural variations in chain length and functional groups [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Most of these compounds have shown various interesting bioactivities such as brine shrimp lethality [1], cytotoxicity [2][3][4][5][6][9][10][11][12][13][14], a-glucosidase inhibition [15] and HIV-1 integrase inhibition [16].…”

Diverse metabolites of coral reef organisms

“…It has three acetylenic bonds on a C 31 chain and resembles the known callyspongins (e.g., 31) [11].…”