Irciniaplysins A-D: New Psammaplysin Derivatives from Philippine Marine Sponge Ircinia sp.

Four new psammaplysin derivatives (1-4) with fatty acyl substituents, designated irciniaplysins A-D, and three known psammaplysins (5-7) were isolated from a marine sponge Ircinia sp. Their structures were elucidated using extensive spectroscopic analyses. The positions of the double bonds and the branch points of the fatty acyl side chains were determined by GC-MS analysis of their fatty acid methyl ester (FAME) derivatives. Irciniaplysins A (1) and B (2) contained an unusual long-chain fatty acyl substituent with a 5,9-diene unit. The isolated compounds were evaluated for their cytotoxic activity against the human colorectal carcinoma (HCT 116) cells, however, none of these compounds showed significant activity.

Experimental verification of fiber coupling characteristics for FSO downlinks from the International Space Station.

Free-space optical (FSO) systems are compulsory to realize high capacity and interference-free communication links from low-Earth orbit (LEO) satellite constellations as well as spacecraft and space stations to the Earth. To be integrated with high-capacity ground networks, the collected portion of the incident beam should be coupled into an optical fiber. To accurately evaluate the signal-to-noise ratio (SNR) and bit-error rate (BER) performance metrics, the probability density function (PDF) of fiber coupling efficiency (CE) must be determined. Previous studies have experimentally verified the CE PDF for a single-mode fiber, however, there is no such investigation for the CE PDF of a multi-mode fiber (MMF) in a LEO-to-ground FSO downlink. In this paper, for the first time, the CE PDF for a 200-µm MMF is experimentally investigated using data from an FSO downlink from the Small Optical Link for International Space Station (SOLISS) terminal to a 40-cm sub-aperture optical ground station (OGS) supported by a fine-tracking system. An average CE of 5.45 dB was also achieved given that the alignment between SOLISS and OGS was not optimal. In addition, using the angle-of-arrival (AoA) and received power data, the statistical characteristics such as channel coherence time, power spectral density, spectrogram, and PDFs of AoA, beam misalignments, and atmospheric turbulence-induced fluctuations are revealed and compared with the state-of-the-art theoretical background.

Polyhydroxy Acids as Fabaceous Plant Components Induce Oviposition of the Common Grass Yellow Butterfly, Eurema Mandarina.

The common grass yellow butterfly, Eurema mandarina is a Fabaceae-feeding species, the females of which readily oviposit on Albizia julibrissin and Lespedeza cuneata in mainland Japan. We previously demonstrated that the methanolic leaf extracts of these plants, and their highly polar aqueous fractions strongly elicit female oviposition. Furthermore, the three subfractions obtained by ion-exchange chromatographic separation of the aqueous fraction have been found to be less effective alone, but synergistically stimulate female oviposition when combined. This indicates that female butterflies respond to multiple compounds with different acidity. We have previously identified d-pinitol from the neutral/amphoteric subfractions and glycine betaine from the basic subfractions as oviposition stimulants of E. mandarina. The present study aimed to identify active compounds in the remaining acidic subfractions of A. julibrissin and L. cuneata leaf extracts. GC-MS analyses of trimethylsilyl-derivatized samples revealed the presence of six compounds in the acidic subfractions. In bioassays using these authentic chemicals, erythronic acid (EA) and threonic acid (TA) were moderately active in eliciting oviposition responses in E. mandarina, with their d-isomers showing slightly higher activity than their l-isomers. Female responsiveness differed between d-EA and l-TA, the major isomers of these compounds in plants, with the response to d-EA reaching a plateau at concentrations above 0.005% and that to l-TA peaking at a concentration of 0.01%. The natural concentrations of d-EA and l-TA in fresh A. julibrissin and L. cuneata leaves were sufficient to stimulate oviposition. Furthermore, mixing 0.001% d-EA or 0.001% l-TA, to which females are mostly unresponsive, with 0.1% d-pinitol resulted in a synergistic enhancement of the oviposition response. These findings demonstrate that E. mandarina females utilize both polyhydroxy acids, EA and TA, as chemical cues for oviposition.

Sex pheromones from male forewings of the Common Grass Yellow Eurema mandarina.

The common grass yellow Eurema mandarina has a characteristic patch (sex brand) composed of specialized scales (androconia) and wing intermembranous cells on the ventral surface of its male forewing. This structure is specific to males and is thought to release compounds that induce female mate acceptance. However, no study has demonstrated that these compounds function as sex pheromones in the genus Eurema. Here we report the identification of sex pheromones in males of E. mandarina. Chemical analyses revealed that 6,10,14-trimethylpentadecan-2-one (TMP) and (E/Z)-3,7,11,15-tetramethylhexadec-2-enal [(E/Z)-phytal] were male-specific and abundant in particular regions of the male forewings. TMP was highest in the sex brand, whereas (E/Z)-phytal was concentrated in the anal cell (cell 2 A), lacking androconia and intermembranous cells. The content of these compounds increases with age in males after emergence. In bioassays, virgin females displayed a posture of bending their abdomens as mating acceptance in response to stimulation by fresh male forewings. However, solvent-washed male wings did not induce such female responses, suggesting that some compounds from male wings serve as triggers. When we examined female responses to compounds applied to solvent-washed male wings, authentic TMP and (E/Z)-phytal alone showed little activity. However, the mixture elicited abdomen-bending responses in one-third of the females. Therefore, TMP and (E/Z)-phytal were found to act synergistically as aphrodisiac sex pheromones for E. mandarina females, although these activities were weak.

Isolation of Fluorescent Benzoxazines with Neuroprotective Activity from the Olive Weevil Pimelocerus perforatus.

The weevil Pimelocerus perforatus poses a serious pest problem for olive cultivation in Japan. Two new racemic fluorescent benzoxazines, designated as pimeforazine A ((±)-1) and pimeforazine B ((±)-2), were successfully isolated from P. perforatus. Their structures, including the absolute configurations of their resolved enantiomers, were determined using spectroscopic methods, single-crystal X-ray diffraction, and electronic circular dichroism calculations. The neuroprotective activity of the isolated compounds was evaluated against hydrogen peroxide-induced cellular damage in SH-SY5Y human neuroblastoma cells. Compounds (±)-1 and (±)-2 exhibited neuroprotective effects.

Chemical Identity of Cuticular Lipid Components in the Mimetic Swallowtail Butterfly Papilio polytes.

The swallowtail Papilio polytes shows Batesian and female-limited polymorphic mimicry. In Japan, P. polytes females have two different forms: the cyrus form is non-mimetic and resembles males, whereas the polytes form mimics Pachliopta aristolochiae and Byasa (Atrophaneura) alcinous as unpalatable models. During mating, P. polytes males use cuticular lipids to distinguish non-mimetic females from conspecific males and sympatric sister species. In this study, we investigated whether compositional differences in cuticular lipids exist between mimetic and non-mimetic females of P. polytes and between mimetic females and their model species. The mimetic and non-mimetic females had nearly identical cuticular lipid profiles, which differed from those of males. The two model species exhibited sexually dimorphic and species-specific cuticular lipid compositions, which were distinctly different from those of mimetic P. polytes females. These results strongly suggest that P. polytes females maintain the identity of cuticular lipid profiles regardless of the mimicry type, and this feature helps males recognize mimetic females as the correct mating partners.

Triterpenoid Saponins from the Fruits of Symplocos lucida as ß-Glucuronidase Inhibitors.

A new triterpenoid saponin and five known ones were isolated from the fruits of Symplocos lucida (Thunb.) Siebold & Zucc. Their structures were determined based on the results of spectroscopy analysis, chemical conversions, and X-ray crystallographic analyses. The ß-glucuronidase-inhibitory effects of the isolated and semi-synthesized triterpenoid saponins were also examined.

Oxygenated Cembrene Diterpenes from Sarcophyton convolutum: Cytotoxic Sarcoconvolutum A-E.

The soft coral genus Sarcophyton contains the enzymatic machinery to synthesize a multitude of cembrene-type diterpenes. Herein, highly oxygenated cembrenoids, sarcoconvolutum A-E (1-5) were purified and characterized from an ethyl acetate extract of the red sea soft coral, Sarcophyton convolutum. Compounds were assemblies according to spectroscopic methods including FTIR, 1D- and 2D-NMR as well as HRMS. Metabolite cytotoxicity was tested against lung adenocarcinoma, cervical cancer, and oral-cavity carcinoma (A549, HeLa and HSC-2, respectively). The most cytotoxic compound, (4) was observed to be active against cell lines A549 and HSC-2 with IC50 values of 49.70 and 53.17 µM, respectively.

Asaroidoxazines from the Roots of Asarum asaroides Induce Apoptosis in Human Neuroblastoma Cells.

Plants in the family Aristolochiaceae contain phenanthrene skeleton-containing chemical constituents that exhibit nephrotoxic, carcinogenic, mutagenic, anti-inflammatory, and cytotoxic effects. Two new phenanthrene-containing 1,2-oxazin-6-ones, designated as asaroidoxazine A (1) and asaroidoxazine B (2), and a known aristolactam, 5-methoxyaristololactam I (3), were isolated from the roots of Asarum asaroides. The structures of compounds 1 and 2 were determined using spectroscopic methods and X-ray crystallography. Treatment of SH-SY5Y human neuroblastoma cells with 1 µM of asaroidoxazine A (1) induced nuclear condensation as well as caspase-3/7 activation, indicating that this compound is a strong apoptosis inducer in neuronal cells. This is the first report of apoptosis induction by phenanthrene-containing oxazines.

The Role of N,N,N-Trimethylglycine in Oviposition of Eurema mandarina on Albizia julibrissin.

The common grass yellow Eurema mandarina (Lepidoptera: Pieridae) uses the silk tree Albizia julibrissin (Fabaceae) as a primary host in Japan. We previously reported that D-pinitol, a cyclitol found in fresh leaves of A. julibrissin, solely elicits moderate oviposition responses from females. However, the aqueous neutral/amphoteric fraction of the fresh leaf extract containing D-pinitol weakly induces oviposition. Moreover, the aqueous neutral/amphoteric/basic fraction was significantly more active than the neutral/amphoteric fraction in eliciting responses, indicating that some basic compounds are involved in stimulating oviposition. High-resolution mass spectrometry and proton nuclear magnetic resonance measurements revealed that the aqueous basic faction contains N,N,N-trimethylglycine (trivial name: glycine betaine) in alkali metal salt form. The average concentration of this quaternary ammonium compound in fresh leaves was estimated to be 0.012% w/w in high performance liquid chromatography analyses. The authentic N,N,N-trimethylglycine induced oviposition at concentrations greater than 0.001% (w/v) and slightly enhanced female responses to the aqueous neutral fraction and authentic D-pinitol. However, its analogues, N,N-dimethylglycine, N-methylglycine, and glycine as well as its precursor choline were inactive. These results demonstrate that N,N,N-trimethylglycine, together with D-pinitol, serves as an stimulant of E. mandarina for oviposition on the leaves of A. julibrissin.

4',6-Dimethoxyisoflavone-7-O-ß-D-glucopyranoside (wistin) is a peroxisome proliferator-activated receptor α (PPARα) agonist in mouse hepatocytes.

Peroxisome proliferator-activated receptors (PPARs) are ligand-dependent transcription factors that regulate lipid and glucose metabolism. PPARα mainly affects fatty acid metabolism, and its activation lowers lipid levels. PPARγ is involved in the regulation of adipogenesis, insulin sensitivity, energy balance, and lipid biosynthesis. We have previously reported that 4',6-dimethoxyisoflavone-7-O-ß-D-glucopyranoside (wistin) can activate PPARγ. The purpose of the present study is to investigate the PPARα agonist activity of wistin. Using a luciferase reporter assay system of PPARα in monkey COS7 kidney cells, we showed that wistin could activate PPARα (P < 0.01 at 10 µg/mL) in a dose-dependent manner. Moreover, the addition of wistin upregulated the expression of PPARα (P < 0.01 at 10 µg/mL) and PPARα target genes including carnitine palmitoyltransferase 1a (P < 0.05 at 10 µg/mL), acyl-CoA oxidase (P < 0.01 at 10 µg/mL), acyl-CoA synthase (P < 0.05 at 10 µg/mL), PPARγ coactivator 1α (P < 0.05 at 10 µg/mL), uncoupling protein 2 (P < 0.05 at 1 µg/mL), and uncoupling protein 3 (P < 0.05 at 10 µg/mL), which are genes involved in lipid efflux and energy expenditure, in mouse primary hepatocytes. Furthermore, wistin inhibited cellular triglyceride accumulation in hepatocytes (P < 0.05 at 10 µg/mL) in a dose-dependent manner. These results indicate that wistin could suppress lipid accumulation through PPARα activation. The action of wistin on PPARα could be of interest for the amelioration of lipid metabolic disorders. To the best of our knowledge, wistin is the first reported isoflavonoid O-glycoside with PPARα agonist activity.

Sulfated Purine Alkaloid Glycosides from the Pupal Case Built by the Bruchid Beetle Bruchidius dorsalis Inside the Seed of Gleditsia japonica.

Three new sulfated isoguanine alkaloid glycosides, designated as saikachinoside A monosulfate (1), saikachinoside A disulfate (2), and locustoside B disulfate (3), have been isolated from the pupal case of the wild bruchid seed beetle Bruchidius dorsalis (Chrysomelidae, Bruchinae) infesting the seed of Gleditsia japonica Miq. (Fabaceae). Their structures were determined by spectroscopic methods and the inhibitory activity of 2 and 3 against acid phosphatase was evaluated.

Cembrene Diterpenoids with Ether Linkages from Sarcophyton ehrenbergi: An Anti-Proliferation and Molecular-Docking Assessment.

Three new cembrene diterpenoids, sarcoehrenbergilid A-C (1-3), along with four known diterpenoids, sarcophine (4), (+)-7α,8ß-dihydroxydeepoxysarcophine (5), sinulolide A (6), and sinulolide B (7), and one steroid, sardisterol (8), were isolated and characterized from a solvent extract of the Red Sea soft coral Sarcophyton ehrenbergi. Chemical structures were elucidated by NMR and MS analyses with absolute stereochemistry determined by X-ray analysis. Since these isolated cembrene diterpenes contained 10 or more carbons in a large flexible ring, conformer stabilities were examined based on density functional theory calculations. Anti-proliferative activities for 1-8 were evaluated against three human tumor cell lines of different origins including the: lung (A549), colon (Caco-2), and liver (HepG2). Sardisterol (8) was the most potent of the metabolites isolated with an IC50 of 27.3 µM against the A549 cell line. Since an elevated human-cancer occurrence is associated with an aberrant receptor function for the epidermal growth factor receptor (EGFR), molecular docking studies were used to examine preferential metabolite interactions/binding and probe the mode-of-action for metabolite-anti tumor activity.

New Prenylated ortho-Dihydroxycoumarins from the Fruits of Ficus nipponica.

Two new prenylated ortho-dihydroxycoumarins, designated fipsomin (1) and fipsotwin (2), were isolated from the fruits of Ficus nipponica together with a known prenylated coumarin, apigravin (3). Their structures were established by spectroscopic data and X-ray crystallographic analysis. Compound 1 exhibited antibacterial activity against Bacillus subtilis with an MIC value of 61 µm, while 2 and 3 showed very weak activity.

D-Pinitol in Fabaceae: an Oviposition Stimulant for the Common Grass Yellow Butterfly, Eurema mandarina.

The common grass yellow butterfly, Eurema mandarina (formerly Eurema hecabe mandarina) (Lepidoptera, Pieridae), recently has been separated taxonomically from a subtropical population of Eurema hecabe in Japan. This species is widely distributed in the temperate region of Japan, and feeds mainly on various ligneous plants within the Fabaceae. We attempted to identify an oviposition stimulant for E. mandarina from its primary hosts, Albizia julibrissin and Lespedeza cuneata. In both hosts, crude extract and an aqueous fraction elicited oviposition responses from gravid females. A polar subfraction of the aqueous fraction also stimulated high oviposition-stimulatory activity, comparable to the original aqueous fraction, suggesting that E. mandarina females use water-soluble compounds for host recognition. Subsequent activity-directed fractionation by ion exchange chromatography indicated that one of the key substances was contained in the neutral/amphoteric fraction. Chemical analyses revealed that the active fractions of both hosts contained D-(+)-pinitol as the major component. We examined female responses to authentic D-pinitol and found that it induced oviposition responses at concentrations greater than 0.1 %. Since this cyclitol is omnipresent in Fabaceae, we conclude that D-pinitol plays a role in mediating oviposition of E. mandarina on fabaceous plants.

Casbane Diterpenes from Red Sea Coral Sinularia polydactyla.

The soft coral genus Sinularia is a rich source of bioactive metabolites containing a diverse array of chemical structures. A solvent extract of Sinularia polydactyla resulted in the isolation of three new casbane diterpenes: sinularcasbane M (1), sinularcasbane N (2) and sinularcasbane O (3); in addition, known metabolites (4-5) were isolated. Compounds were elucidated on the basis of spectroscopic analyses; the absolute configuration was confirmed by X-ray analysis.

New terpenes from the Egyptian soft coral Sarcophyton ehrenbergi.

Chemical investigations of the Egyptian soft coral Sarcophyton ehrenbergi have led to the isolation of compounds 1-3 as well as the previously reported marine cembranoid diterpene sarcophine (4). Structures were elucidated by comprehensive NMR and HRMS experimentation. Isolated compounds were in vitro assayed for cytotoxic activity against human hepatocarcinoma (HepG2) and breast adenocarcinoma (MCF-7) cell lines.

Dorsamin-A's, glycerolipids carrying a dehydrophenylalanine ester moiety from the seed-eating larvae of the bruchid beetle Bruchidius dorsalis.

Using a TLC autographic assay for radical-scavenging activity with the ABTS radical, the presence of lipophilic antioxidants in the larvae of the wild bruchid seed beetle Bruchidius dorsalis was detected. Assay-guided fractionation of the CHCl3-soluble fraction of the larvae resulted in the isolation of new glycerolipids, designated dorsamin-A763, -A737, -A765, -A739, and -A767, comprising 1,2-diacyl-sn-glycero-3-dehydrophenylalanine ester structural units. The ABTS radical scavenging activity of the dorsamin-A's was comparable with or stronger than that of Trolox.

New guaianolide-type sesquiterpene lactones from Inula verbascifolia.

The aerial parts of Inula verbascifolia afforded two new guaianolide-type sesquiterpene lactones. Their structures were determined by spectroscopic methods (IR, MS, 1H NMR, 13C NMR, DEPT, 1H-1H COSY, HMQC, and HMBC).