New cerebrosides from the basidiomycete <Emphasis Type="Italic">Cortinarius tenuipes</Emphasis>

Five cerebrosides (1–5), including three new ones named cortenuamide A (1), cortenuamide B (2), and cortenuamide C (3), were isolated from the fruiting bodies of the basid-iomycete Cortinarius tenuipes. The structures of those compounds were elucidated as (4E,8E)-N-d-2′-hydroxytetracosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (1), (4E,8E)-N-d-2′-hydroxytricosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8 sphingadienine (2), (4E, 8E)-N-d-2′-hydroxydocosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (3), (4E, 8E)-N-d-2′-hydroxyoctadecanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (4), and (4E, 8E)-N-d-2′-hydroxypalmitoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (5) by spectral and chemical methods.     

<Emphasis Type="Italic">Santalum </Emphasis><Emphasis Type="Italic">insulare</Emphasis> Acetylenic Fatty Acid Seed Oils: Comparison within the <Emphasis Type="Italic">Santalum</Emphasis> Genus

The sandalwood kernels of Santalum insulare (Santalaceae) collected in French Polynesia give seed oils containing significant amounts of ximenynic acid, E-11-octadecen-9-oic acid (64–86%). Fatty acid (FA) identifications were performed by gas chromatography/mass spectrometry (GC/MS) of FA methyl esters. Among the other main eight identified fatty acids, oleic acid was found at a 7–28% level. The content in stearolic acid, octadec-9-ynoic acid, was low (0.7–3.0%). An inverse relationship was demonstrated between ximenynic acid and oleic acid using 20 seed oils. Results obtained have been compared to other previously published data on species belonging to the Santalum genus, using multivariate statistical analysis. The relative FA S. insulare composition, rich in ximenynic acid is in the same order of those given for S. album or S. obtusifolium. The other compared species (S. acuminatum, S. lanceolatum, S. spicatum and S. murrayanum) are richer in oleic acid (40–59%) with some little differences in linolenic content.     

Synthesis of <Emphasis Type="Italic">p</Emphasis><Emphasis Type="Bold">-</Emphasis> and <Emphasis Type="Italic">n</Emphasis>-type Gels Doped with Ionic Charge Carriers

In this study, we synthesized the new kinds of semiconducting polymeric gels having negative (n-type) and positive (p-type) counter ions as charge carriers. The polyacrylamide gel was doped with pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt), having \textSO₃ ^- {\text{SO}}_{3}^{ - } ions as side groups and Na⁺ as counter ions, so-called p-type semiconducting gel. The doping process was performed during the polymerization where the pyranine binds to the polymer strands over OH group chemically via radical addition. In a similar way, N-isopropylacrylamide (NIPA) gel was doped with methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), having Cl⁻ as counter ions, so-called n-type semiconducting gel. Here MAPTAC was embedded by copolymerization within the polymer network (NIPA). These semiconducting gels can show different electrical properties by changing the concentration of the doping agents, swelling ratio etc. We have shown that the pn junction, formed by combining p-type and n-type gels together in close contact, rectifies the current similar to the conventional Si and Ge diodes.     

(1<Emphasis Type="Italic">S</Emphasis>,3<Emphasis Type="Italic">R</Emphasis>)-<Emphasis Type="Italic">cis</Emphasis>-Chrysanthemyl Tiglate: Sex Pheromone of the Striped Mealybug, <Emphasis Type="Italic">Ferrisia virgata</Emphasis>

Derivatives of 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid (chrysanthemic acid) are classic natural pyrethroids discovered in pyrethrum plants and show insecticidal activity. Chrysanthemic acid, with two asymmetric carbons, has four possible stereoisomers, and most natural pyrethroids have the (1R,3R)-trans configuration. Interestingly, chrysanthemic acid–related structures are also found in insect sex pheromones; carboxylic esters of (1R,3R)-trans-(2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropyl)methanol (chrysanthemyl alcohol) have been reported from two mealybug species. In the present study, another ester of chrysanthemyl alcohol was discovered from the striped mealybug, Ferrisia virgata (Cockerell), as its pheromone. By means of gas chromatography–mass spectrometry, nuclear magnetic resonance spectrometry, and high-performance liquid chromatography analyses using a chiral stationary phase column and authentic standards, the pheromone was identified as (1S,3R)-(?)-cis-chrysanthemyl tiglate. The (1S,3R)-enantiomer strongly attracted adult males in a greenhouse trapping bioassay, whereas the other enantiomers showed only weak activity. The cis configuration of the chrysanthemic acid–related structure appears to be relatively scarce in nature, and this is the first example reported from arthropods.     

Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

Comparison of Postprandial Oleic Acid, 9<Emphasis Type="Italic">c,</Emphasis>11<Emphasis Type="Italic">t</Emphasis> CLA and 10<Emphasis Type="Italic">t,</Emphasis>12<Emphasis Type="Italic">c</Emphasis> CLA Oxidation in Healthy Moderately Overweight Subjects

Few studies report the individual effect of 9c,11t- and 10t,12c-CLA on human energy metabolism. We compared the postprandial oxidative metabolism of 9c,11t- and 10t,12c-CLA and oleic acid (9c-18:1) in 22 healthy moderately overweight volunteers. After 24 weeks supplementation with 9c,11t-, 10t,12c-CLA or 9c-18:1 (3 g/day), subjects consumed a single oral bolus of the appropriate [1-¹³C]-labeled fatty acid. 8 h post-dose, cumulative oxidation was similar for 9c-18:1 and 10t,12c (P = 0.66), but significantly higher for 9c,11t (P < 0.01).     

Biosynthesis of (3<Emphasis Type="Italic">Z</Emphasis>,6<Emphasis Type="Italic">Z</Emphasis>,9<Emphasis Type="Italic">Z</Emphasis>)-3,6,9-Octadecatriene: The Main Component of the Pheromone Blend of <Emphasis Type="Italic">Erannis bajaria</Emphasis>

The hydrocarbons (3Z,6Z,9Z)-3,6,9-octadecatriene (3Z,6Z,9Z-18:H) and (3Z,6Z,9Z)-3,6,9-nonadecatriene (3Z,6Z,9Z-19:H) constitute the pheromone of the winter moth, Erannis bajaria. These compounds belong to a large group of lepidopteran pheromones which consist of unsaturated hydrocarbons and their corresponding oxygenated derivatives. The biosynthesis of such hydrocarbons with an odd number of carbons in the chain is well understood. In contrast, knowledge about the biosynthesis of even numbered derivatives is lacking. We investigated the biosynthesis of 3Z,6Z,9Z-18:H by applying deuterium-labeled precursors to females of E. bajaria followed by gas chromatography–mass spectrometry analysis of extracts of the pheromone gland. A mixture of deuterium-labeled [17,17,18,18-²H₄]-3Z,6Z,9Z-18:H and the unlabeled 3Z,6Z,9Z-18:H was obtained after topical application and injection of (10Z,13Z,16Z)-[2,2,3,3-²H₄]-10,13,16-nonadecatrienoic acid ([2,2,3,3-²H₄]-10Z,13Z,16Z-19:acid) or (11Z,14Z,17Z)-[3,3,4,4-²H₄]-11,14,17-icosatrienoic acid ([3,3,4,4-²H₄]-11Z,14Z,17Z-20:acid). These results are consistent with a biosynthetic pathway that starts with α-linolenic acid (9Z,12Z,15Z-18:acid). Chain elongation leads to 11Z,14Z,17Z-20:acid, which is shortened by α-oxidation as the key step to yield 10Z,13Z,16Z-19:acid. This acid can be finally reduced to an aldehyde and decarbonylated or decarboxylated to furnish the pheromone component 3Z,6Z,9Z-18:H. A similar transformation of 11Z,14Z,17Z-20:acid yields the second pheromone component, 3Z,6Z,9Z-19:H.     

Laboratory Evaluation of <Emphasis Type="Italic">Artemisia annua</Emphasis> L. Extract and Artemisinin Activity against <Emphasis Type="Italic">Epilachna paenulata</Emphasis> and <Emphasis Type="Italic">Spodoptera eridania</Emphasis>

Ethanolic extract of aerial parts of Artemisia annua L. and artemisinin were evaluated as anti-insect products. In a feeding deterrence assay on Epilachna paenulata Germ (Coleoptera: Coccinellidae) larvae, complete feeding rejection was observed at an extract concentration of 1.5 mg/cm² on pumpkin leaf tissue. The same concentration produced a feeding inhibition of 87% in Spodoptera eridania (Cramer) (Lepidoptera: Noctuidae). In a no-choice assay, both species ate less and gained less weight when fed on leaves treated with the extract. Complete mortality in E. paenulata and 50% mortality in S. eridania were observed with extract at 1.5 mg/cm². Artemisinin exhibited a moderate antifeedant effect on E. paenulata and S. eridania at 0.03–0.375 mg/cm². However, a strong effect on survival and body weight was observed when E. paenulata larvae were forced to feed on leaves treated at 0.03 and 0.075 mg/cm². Artemisia annua ethanolic extract of aerial parts at 1.5 mg/cm² showed no phytotoxic effect on pumpkin seedlings.     

Solvent-gradient SMB to separate <Emphasis Type="Italic">o</Emphasis>-xylene and <Emphasis Type="Italic">p</Emphasis>-xylene

In batch chromatography, solvent-gradient operations (SG) produce significant improvement in terms of the enrichment of products and the separation time and the solvent consumption as compared with isocratic operations. This work studied solvent-gradient operation in reversed-phase simulated moving bed unit to separate ortho-xylene and para-xylene. In a solvent-gradient mode, different mobile phase compositions lead to a different retention behavior of solutes, i.e., different adsorption isotherms. Frontal analysis experiments for ortho-xylene and para-xylene were carried out with a reversed-phase column to measure adsorption parameters at several different mobile phase compositions, such as 45%, 50%, 60%, 75% and 90% acetonitrile. Therefore, the parameters in the retention model for solvent-gradient operation in the case of reversed-phase chromatography were estimated and applied to the design of an SMB system. A modified design method for solvent-gradient simulated moving bed chromatography (SG-SMB) was proposed. The robust operating conditions were obtained within the separation region on (φ _R , φ _E ) plane (φ _R and φ _E are the volumetric content of organic modifier in the raffinate and the extract streams, respectively). The performance results of isocratic and solvent-gradient SMB were compared. A partial-discard strategy and increasing of the solvent gradient level were also applied to improve the performance of the SG-SMB.     

Ferrocenyl Monomers and Polymers of <Emphasis Type="Italic">N</Emphasis>-Allyl and <Emphasis Type="Italic">N</Emphasis>-Acrylatenaphthalimides

A series of N-allyl, N-ethylmethacrylate and N-phenylmethacrylatenaphthalimide monomers have been prepared with –C=CFc, –C≡CFc and –C≡CSiMe₃ substituents at the 4-position of the naphthalimide ring. All have been characterised by elemental analysis and spectroscopy; the X-ray structure of N-allyl-4-ethenylferrocenylnapththalimide is also reported. Free-radical polymerisation of these monomers gave homopolymers, random co- and terpolymers with polydispersities ranging from 1.7 to 3.2. Incorporation into a polymer matrix has no effect on the spectroscopic and electrochemical properties of the naphthalimide or ferrocenyl components. The ferrocenyl polymers are electrochromic and when oxidised give naphthalimide charge-transfer bands in the NIR; this electrochromism was examined by OTTLE techniques.     

Yellow-Cedar, <Emphasis Type="Italic">Callitropsis</Emphasis> (<Emphasis Type="Italic">Chamaecyparis</Emphasis>) <Emphasis Type="Italic">nootkatensis</Emphasis>, Secondary Metabolites,Biological Activities,and Chemical Ecology

Yellow-cedar, Callitropsis nootkatensis, is prevalent in coastal forests of southeast Alaska, western Canada, and inland forests along the Cascades to northern California, USA. These trees have few microbial or animal pests, attributable in part to the distinct groups of biologically active secondary metabolites their tissues store for chemical defense. Here we summarize the new yellow-cedar compounds identified and their biological activities, plus new or expanded activities for tissues, extracts, essential oils and previously known compounds since the last review more than 40 years ago. Monoterpene hydrocarbons are the most abundant compounds in foliage, while heartwood contains substantial quantities of oxygenated monoterpenes and oxygenated sesquiterpenes, with one or more tropolones. Diterpenes occur in foliage and bark, whereas condensed tannins have been isolated from inner bark. Biological activities expressed by one or more compounds in these groups include fungicide, bactericide, sporicide, acaricide, insecticide, general cytotoxicity, antioxidant and human anticancer. The diversity of organisms impacted by whole tissues, essential oils, extracts, or individual compounds now encompasses ticks, fleas, termites, ants, mosquitoes, bacteria, a water mold, fungi and browsing animals. Nootkatone, is a heartwood component with sufficient activity against arthropods to warrant research focused toward potential development as a commercial repellent and biopesticide for ticks, mosquitoes and possibly other arthropods that vector human and animal pathogens.     

Effects of Root Isoquinoline Alkaloids from <Emphasis Type="Italic">Hydrastis canadensis</Emphasis> on <Emphasis Type="Italic">Fusarium oxysporum</Emphasis> Isolated from <Emphasis Type="Italic">Hydrastis</Emphasis> Root Tissue

Goldenseal (Hydrastis canadensis L.) is a popular medicinal plant distributed widely in North America. The rhizome, rootlets, and root hairs produce medicinally active alkaloids. Berberine, one of the Hydrastis alkaloids, has shown antifungal activity. The influence of a combination of the major Hydrastis alkaloids on the plant rhizosphere fungal ecology has not been investigated. A bioassay was developed to study the effect of goldenseal isoquinoline alkaloids on three Fusarium isolates, including the two species isolated from Hydrastis rhizosphere. The findings suggest that the Hydrastis root extract influences macroconidia germination, but that only the combined alkaloids—berberine, canadine, and hydrastine—appear to synergistically stimulate production of the mycotoxin zearalenone in the Fusarium oxysporum isolate. The Hydrastis root rhizosphere effect provided a selective advantage to the Fusarium isolates closely associated with the root tissue in comparison with the Fusarium isolate that had never been exposed to Hydrastis.     

(<Emphasis Type="Italic">Z</Emphasis>)-Pentacos-12-ene,an Oviposition-deterring Pheromone of <Emphasis Type="Italic">Cheilomenes sexmaculata</Emphasis>

Larvae of the coccinellid beetle Cheilomenes sexmaculata (F.) produce an oviposition-deterring pheromone that inhibits egg laying of conspecific females on oviposition sites walked over by first-instar larvae. By use of bioassay-guided fractionation of larval extracts, (Z)-pentacos-12-ene was identified as an active component of the cuticular hydrocarbons of the larvae. Other compounds that occur in the active fractions, such as the alkaloid coccinelline and saturated hydrocarbons, were individually tested but proved to be inactive. The synthesis of (Z)-pentacos-12-ene is reported.     

Cyanolipid-rich seed oils from <Emphasis Type="Italic">Allophylus natalensis</Emphasis> and <Emphasis Type="Italic">A. dregeanus</Emphasis>

As a continuation of our study on plants of the Sapindaceae, the chemical composition of the oil extracted from seeds of Allophylus natalensis (Sonder) De Winter and of A. dregeanus (Sonder) De Winter has been investigated. The oil from both species contained approximately equal amounts of TAG and type I cyanolipids (CL), 1-cyano-2-hydroxymethylprop-2-en-1-oldiesters, with minor amounts of type III CL, 1-cyano-2-hydroxymethylprop-1-en-3-ol-diesters. Structural investigation of the oil components was accomplished by chemical, chromatographic (TLC, CC, GC, and GC-MS), and spectroscopic (IR, NMR) means. GC and GC-MS analysis showed that C₂₀ FA were dominant in the CL components of the oil from the two species (44–80% vs. 21–26% in TAG), with cis-11-eicosenoic acid (36–46%) and cis 13-eicosenoic acid (paullinic acid, 23–37%) as the major esterified fatty acyl chains in A. natalensis and A. dregeanus, respectively. cis-Vaccenic acid was particularly abundant (11–31%) in the CL from A. dregeanus, whereas eicosanoic acid (10–22%) was also a major component of CL in both species.     

<Emphasis Type="Italic">N</Emphasis>-Acylated Bacteriohopanehexol-Mannosamides from the Thermophilic Bacterium <Emphasis Type="Italic">Alicyclobacillus acidoterrestris</Emphasis>

Identification of molecular species of various N-acylated bacteriohopanehexol-mannosamides from the thermophilic bacterium Alicyclobacillus acidoterrestris by semipreparative HPLC and by RP-HPLC with ESI is described. We used triple-quadrupole type mass spectrometer, ¹H and ¹³C NMR for analyzing this complex lipid. CD spectra of two compounds (model compound—7-deoxy-d-glycero-d-allo-heptitol obtained by stereospecific synthesis, and an isolated derivative of hopane) were also measured and the absolute configuration of both compounds was determined. On the basis of all the above methods, we identified the full structure of a new class of bacteriohopanes, represented by various N-acylated bacteriohopanehexol-mannosamides.     

Mechanical and thermal characterization of <Emphasis Type="Italic">cis</Emphasis>-polyisoprene and <Emphasis Type="Italic">trans</Emphasis>-polyisoprene blends

Measurements of mechanical and thermal transport properties have been made on the blends of cis-polyisoprene (CPI) and trans-polyisoprene (TPI) prepared by a solution casting method. Characterization of these blends has been done using wide angle X-ray scattering. Thermo-mechanical, mechanical, and thermal transport properties have been determined employing dynamic mechanical analyzer (DMA) and transient plane source. Storage modulus and tan δ as determined from DMA have been found to increase and decrease with the increase in TPI content, respectively. Mechanical properties such as Young’s modulus and tensile strength, as determined from strain–stress behavior of CPI/TPI blends, have been found to increase with increasing TPI content. This increase in properties has been explained on the basis of the crosslink density, calculated using theory of rubber elasticity. Thermal transport properties such as thermal conductivity, thermal diffusivity, and volumetric heat capacity are higher for all the three blends as compared to their pure components.     

Chemical Composition and Nutritional Characteristics of the Seed Oil of Wild <Emphasis Type="Italic">Lathyrus</Emphasis>, <Emphasis Type="Italic">Lens</Emphasis> and <Emphasis Type="Italic">Pisum</Emphasis> Species from Southern Spain

The fatty acid composition of the seed oil of 19 wild legume species from southern Spain was analyzed by gas chromatography. The main seed oil fatty acids ranged from C_14:0 to C_20:0. Among unsaturated fatty acids, the most abundant were linoleic, oleic and linolenic acids, except for Lathyrus angulatus, L. aphaca, L. clymenum, L. sphaericus and L. nigricans where C_18:3 contents were higher than C_18:1 contents. Palmitic acid was the most abundant saturated acid in studied species, ranging from 11.6% in Lathyrus sativus to 19.3% in Lens nigricans. All studied species showed higher amounts of total unsaturated fatty acids than saturated ones. Among studied species, the ω6/ω3 ratio was variable, ranging from 2.0% in L. nigricans to 13.8% in L. sativus, there being eight species in which the ω6/ω3 ratio was below 5. The fatty acids observed in these plants supports the use of these plants as a source of important dietary lipids.     

Relationship Between the Endophyte <Emphasis Type="Italic">Embellisia</Emphasis> spp. and the Toxic Alkaloid Swainsonine in Major Locoweed Species (<Emphasis Type="Italic">Astragalus</Emphasis> and <Emphasis Type="Italic">Oxytropis)</Emphasis>

Locoweeds (Astragalus and Oxytropis spp. that contain the toxic alkaloid swainsonine) cause widespread poisoning of livestock on western rangelands. There are 354 species of Astragalus and 22 species of Oxytropis in the US and Canada. Recently, a fungal endophyte, Embellisia spp., was isolated from Astragalus and Oxytropis spp. and shown to produce swainsonine. We conducted a survey of the major locoweeds from areas where locoweed poisoning has occurred to verify the presence of the endophyte and to relate endophyte infection with swainsonine concentrations. Species found to contain the fungal endophyte and produce substantial amounts of swainsonine were A. wootoni, A. pubentissimus, A. mollissimus, A. lentiginosus, and O. sericea. Astragalus species generally had higher concentrations of swainsonine than Oxytropis. Swainsonine was not detected in A. alpinus, A. cibarius, A. coltonii, A. filipes, or O. campestris. The endophyte could not be cultured from A. mollissimus var. thompsonii or A. amphioxys, but was detected by polymerase chain reaction, and only 30% of these samples contained trace levels of swainsonine. Further research is necessary to determine if the endophyte is able to colonize these and other species of Astragalus and Oxytropis and determine environmental influences on its growth and synthesis of swainsonine.     

Altered Lipid Response in Hamsters Fed <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11+<Emphasis Type="Italic">trans</Emphasis>-8,<Emphasis Type="Italic">cis</Emphasis>-10 Conjugated Linoleic Acid Mixture

The objective of the present study was to compare the effects of cis-9,trans-11 + trans-8,cis-10 conjugated linoleic acid (CLA) mixture to those of cis-9,trans-11 + trans-10,cis-12 CLA mixture and linoleic acid (LA) on lipoprotein profile, hepatic lipids, body composition and digestibility of dietary fat in hamsters (n = 17) fed diets containing 2% of experimental fat (w/w) for 28 days. The cis-9,trans-11 + trans-10,cis-12 CLA mixture showed higher LDL cholesterol concentrations than LA and the cis-9,trans-11 + trans-8,cis-10 CLA mixture. The cis-9,trans-11 + trans-8,cis-10 CLA mixture induced similar plasma LDL cholesterol and hepatic lipid concentrations, and coefficient of digestibility as LA, indicating no effect of the trans-8,cis-10 CLA isomer on these lipid parameters. On the other hand, the cis-9,trans-11 + trans-8,cis-10 CLA mixture induced higher plasma VLDL cholesterol and triglycerides than LA and the cis-9,trans-11 + trans-10,cis-12 CLA mixture. The cis-9,trans-11 + trans-8,cis-10 CLA mixture also induced the highest plasma glucose concentrations compared with the two other groups, indicating an impairment of glycemic control. No differences in body composition were noted between the three groups. The present results thus show that the cis-9,trans-11 + trans-8,cis-10 CLA mixture can deteriorate plasma VLDL cholesterol and triglycerides in hamsters, possibly due to an increased flux of glucose.     

Parameters for optimization of coke quality (<Emphasis Type="Italic">CRI</Emphasis> and <Emphasis Type="Italic">CSR</Emphasis>)

Experimental data illustrate the diversity of ash composition in Russian coal, even within a single rank. Examples show that the ash basicity may be used for effective optimization of the coking-batch composition by basin, rank, and components, in improving the CRI and CSR values of coke.