Differences in Sterol Composition between Male and Female Gonads of Dominant Limpet Species

The present study demonstrated here for the first time that there are statistically significant differences in sterol composition between male and female gonads of the dominant limpets Cellana grata and Cellana toreuma, which are intertidal gastropods. Among 11 different sterols identified in this study, unusually high levels (11.2–19.8% of total sterols) of the Δ⁸-sterols 5α-cholest-8-en-3β-ol (zymostenol) and 5α-cholesta-8,24-dien-3β-ol (zymosterol), which have never been reported in aquatic invertebrate gonads, were present in only the male gonads.     

Total Synthesis and Structural Elucidation of Two Unusual Non-Methylene-Interrupted Fatty Acids in Ovaries of the Limpet <Emphasis Type="Italic">Cellana toreuma</Emphasis>

In our previous study, unusual odd‐numbered dienoic acids with a terminal olefin were found as minor components in ovaries of the Japanese limpet Cellana toreuma, and the synthetic interests have been focused onto their structural confirmation and the inspection into their potential biological activity. Here, we describe an efficient and stereoselective total synthesis of two new unusual dienoic acids, 19:2?7,18 and 21:2?7,20, through a common pathway involving the strategic combination of alkyne‐zipper reaction and Lindlar hydrogenation for the construction of their unique carbon chains. In our synthetic study, 2‐propyn‐1‐ol was at first subjected to alkylation and alkyne‐zipper reaction to form the two fragments, and the subsequent carbon chain elongation was achieved by the usual coupling reaction to obtain the C‐19 and C‐21 products bearing an internal acetylenic group. Then, the internal acetylenic group of these products was subjected to Lindlar hydrogenation to form a Z‐alkenyl moiety, and the subsequent deprotection of the products was carried out under an acidic condition without isomerization of the internal Z‐alkenyl group. Total synthesis of target fatty acids, 19:2?7,18 and 21:2?7,20, was finally accomplished by two‐step oxidation of the resulting alcohols into carboxylic acids in a highly chemoselective manner, and the structures of these unusual natural fatty acids were finally elucidated by identifying the GC–MS spectra of the methyl esters of authentic and synthetic fatty acids.     

Novel Odd-Chain Fatty Acids with a Terminal Double Bond in Ovaries of the Limpet <Emphasis Type="Italic">Cellana toreuma</Emphasis>

Our previous study characterized highly diverse dienoic fatty acids (FA), in particular an uncommon non‐methylene‐interrupted (NMI) FA, in the ovaries of the Japanese limpet Cellana toreuma belonging to the archaeogastropods, but many minor chemically unidentified FA remain. In this study, among previously unidentified FA (less than 0.1% of total FA), four novel NMI FA with a terminal double bond [7,18‐nonadecadienoic (19:2Δ7,18), 11,18‐nonadecadienoic (19:2Δ11,18), 7,20‐heneicosadienoic (21:2Δ7,20), and 11,20‐heneicosadienoic (21:2Δ11,20) acids] were found, along with known 14‐pentadecenoic (15:1Δ14), 16‐heptadecenoic (17:1Δ16), and 9,18‐nonadecadienoic (19:2Δ9,18) acids, based on capillary GC–MS of their methyl esters, 3‐pyridylcarbinol derivatives, and argentation thin‐layer chromatography. From our findings, possible biosynthetic pathways for the novel FA are discussed.     

The Diversity of Health Effects of Individual <Emphasis Type="Italic">trans</Emphasis> Fatty Acid Isomers

There are multiple adverse effects of trans fatty acids (TFA) that are produced by partial hydrogenation (i.e., manufactured TFA), on CVD, blood lipids, inflammation, oxidative stress, endothelial health, body weight, insulin sensitivity, and cancer. It is not yet clear how specific TFA isomers vary in their biological activity and mechanisms of action. There is evidence of health benefits on some of the endpoints that have been studied for some animal TFA isomers, such as conjugated linoleic acid; however, these are not a major TFA source in the diet. Future research will bring clarity to our understanding of the biological effects of the individual TFA isomers. At this point, it is not possible to plan diets that emphasize individual TFA from animal sources at levels that would be expected to have significant health effects. Due to the multiple adverse effects of manufactured TFA, numerous agencies and governing bodies recommend limiting TFA in the diet and reducing TFA in the food supply. These initiatives and regulations, along with potential TFA alternatives, are presented herein.     

<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.     

Phospholipid Composition of <Emphasis Type="Italic">Jatropha curcus</Emphasis> Seed Lipids

Jatropha curcus L. oil has emerged as one of the most important raw materials for biodiesel production. However, no detailed study has been reported on characterizing the lipid constituents of jatropha oil. The present study revealed that the total oil content of jatropha seeds was 32% with a composition of 97.6% neutral lipids, 0.95% glycolipids and 1.45% phospholipids. The fatty acid composition of total lipids, neutral lipids, phospholipids and glycolipids was also determined and found to contain oleic acid (18:1) and linoleic acids (18:2) as major fatty acids. The phospholipids fraction was further characterized and quantified and found to contain phosphatidyl choline (PC) 60.5%, phosphatidyl inositol (PI) 24% and phosphatidyl ethanolamine (PE) 15.5%. The fatty acid composition and the positional distribution of the fatty acids of individual phospholipids were also reported.     

Lipid Classes and Fatty Acid Composition of the Tropical Nudibranch Mollusks <Emphasis Type="Italic">Chromodoris</Emphasis> sp. and <Emphasis Type="Italic">Phyllidia coelestis</Emphasis>

Two nudibranch mollusks, Chromodoris sp. and Phyllidia coelestis, collected from tropical waters of the Northwestern Pacific, were analyzed for lipids. The aim of this study was to fill the gap in knowledge of lipid biochemistry of mollusks. Phospholipids (PL) were the dominating lipid class followed by sterols (13%). Neutral lipids were not detected in Chromodoris sp. By contrast, P. coelestis contained TAG, diacylglyceryl ether, long chain alcohol and esters of sterols. Among PL, PC was predominant (about 50%); PE, PS and CAEP were almost in equal proportions. Sixty five FA were identified as methyl esters and N-acyl pyrrolidides by GC-MS. The sea slugs exhibited a wide diversity of FA. The common marine n-3 PUFA, 20:5n-6 and 22:6n-3, constituted 0.6-1.3% of the total FA, whereas n-6 PUFA, 22:4n-6, 20:4n-6, and 18:2n-6, were the main (25%). Among monounsaturated FA, 7-21:1 was the main (up to 6.2%). The non-methylene-interrupted (NMI) FA were found (9.4 and 12.4%), including the known 5,11-20:2, 5,13-20:2, 7,13-22:2, 7,15-22:2 and a novel isomer 7,13-21:2 (up to 3.9%). The pathway of its biosynthesis was suggested. A series of very long chain FA (VLC FA), with the main 5,9-25:2 and 5,9-26:2, were identified. High level of VLC FA (8.7 and 11.7%) in sea slugs is apparently the result of predation on sponges. Another unique feature concerned a high abundance of various odd and branched FA (16.7 and 34%), which could have originated from the dietary origin or symbiotic bacteria. This is the first report on lipid and FA composition of nudibranchs.     

Fatty Acid Composition of Turkish <Emphasis Type="Italic">Rhododendron</Emphasis> Species

This study describes work aimed at the rapid evaluation of the fatty acid (FA) composition of Turkish Rhododendron species, particularly the leaves and the flowers of the toxic plants, R. ponticum and R. luteum. The FA profiles of the available parts of three other nonpoisonous Rhododendron species were also investigated. Subtotal extracts obtained (using n-hexane, chloroform and methanol) from total chloroform:methanol (1:1) extracts were analyzed and compared to each other. Palmitic acid was found to be the most abundant FA in almost all Rhododendron extracts, and the majority of leaf and flower extracts contained significant portions of C18 unsaturated FAs (18:1n-9, 18:2n-6, 18:3n-3). The n-hexane extracts of R. ponticum leaves and R. luteum flowers were unique, as they contained an unusual series of even-chain iso FAs (C16–C24). Especially the n-hexane extracts were found to comprise uncommon FAs with odd-numbered carbons (C13–C29). Overall, n-hexane proved to be the best solvent by representing the richest FA profile, whereas chloroform or methanol appeared less suitable for FA analyses. Appreciable intra-species variations in FA compositions among the leaves as well as other anatomical parts examined were observed. This study highlights the chemotaxonomical importance of the FAs for the genus Rhododendron.     

Preparative Separation of <Emphasis Type="Italic">cis</Emphasis>- and <Emphasis Type="Italic">trans</Emphasis>-Isomers of Unsaturated Fatty Acid Methyl Esters Contained in Edible Oils by Reversed-Phase High-Performance Liquid Chromatography

In order to measure exactly the trans-fatty acids content in food materials, a preparative group separation of cis- and trans-isomers of unsaturated fatty acid methyl esters (FAMEs) was achieved by an isocratic reversed-phase HPLC (RP-HPLC) method. The trans-isomers of 16:1, 18:1, 18:2, 18:3, 20:1 and 22:1 FAMEs were readily separated from the corresponding cis-isomers by a COSMOSIL Cholester C18 column (4.6 mm I.D. × 250 mm, Nacalai Tesque) or a TSKgel ODS-100Z column (4.6 mm I.D. × 250 mm, TOSOH), using acetonitrile as the mobile phase. This method was applied for determining the trans-18:1 fatty acid content in partially hydrogenated rapeseed oil. The methyl esters of cis- and trans-18:1 isomers of the oil were collected as two separate fractions by the developed RP-HPLC method. Each fraction was analyzed by gas chromatography (GC) for both qualitative and quantitative information on its positional isomers. By a combination of RP-HPLC and GC methods, a nearly complete separation of cis- and trans-18:1 positional isomers was achieved and the trans-18:1 fatty acid content was able to be evaluated more precisely than is possible by the direct GC method. The reproducibility of cis- and trans-18:1 isomers fractionated by the RP-HPLC method was better than 98%. These results suggested that the preparative RP-HPLC method developed in this study could be a powerful tool for trans-fatty acid analysis in edible oils and food products as an alternative to silver-ion chromatography.     

Plant Growth Inhibition By <Emphasis Type="Italic">Cis</Emphasis>-Cinnamoyl Glucosides and <Emphasis Type="Italic">Cis</Emphasis>-Cinnamic Acid

Spiraea thunbergii Sieb. contains 1-O-cis-cinnamoyl--_d-glucopyranose (CG) and 6-O-(4-hydroxy-2-methylene-butyroyl)-1-O-cis-cinnamoyl--_d-glucopyranose (BCG) as major plant growth inhibiting constituents. In the present study, we determined the inhibitory activity of CG and BCG on root elongation of germinated seedlings of lettuce (Lactuca sativa), pigweed (Amaranthus retroflexus), red clover (Trifolium pratense), timothy (Phleum pratense), and bok choy (Brassica rapa var chinensis) in comparison with that of two well-known growth inhibitors, 2,4-dichlorophenoxyacetic acid (2,4-D) and (+)-2-cis-4-trans-abscisic acid (cis-ABA), as well as two related chemicals of CG and BCG, cis-cinnamic acid (cis-CA) and trans-cinnamic acid (trans-CA). The EC₅₀ values for CG and BCG on lettuce were roughly one-half to one-quarter of the value for cis-ABA. cis-Cinnamic acid, which is a component of CG and BCG, possessed almost the same inhibitory activity of CG and BCG, suggesting that the essential chemical structure responsible for the inhibitory activity of CG and BCG is cis-CA. The cis-stereochemistry of the methylene moiety is apparently needed for high inhibitory activity, as trans-CA had an EC₅₀ value roughly 100 times that of CG, BCG, and cis-CA. Growth inhibition by CG, BCG, and cis-CA was influenced by the nature of the soil in the growing medium: alluvial soil preserved the bioactivity, whereas volcanic ash and calcareous soils inhibited bioactivity. These findings indicate a potential role of cis-CA and its glucosides as allelochemicals for use as plant growth regulators in agricultural fields.     

Hybrid <Emphasis Type="Italic">Hibiscus</Emphasis> seed oil compositions

The seeds of cultivated Hibiscus spp. were extracted with supercritical carbon dioxide, and the resulting extracts were analyzed to identify the major TG components as the corresponding FAME. The seed oils were composed predominantly of oleic and linoleic FA (69.6–83.4%) with lesser amounts of palmitic acid (14.8–27.0%). Minor amounts of C14, C18, and C20 saturated FA were also detected. The oil content of the seeds was determined to be between 11.8 and 22.1 wt% for hybrid varieties and between 8.9 and 29.5 wt% for the native species from which the hybrid varieties were developed. The protein content of the defatted seed meal averaged 20% for the hybrid varieties. The composition of the extracted hibiscus seed oils suggests potential edible applications.     

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.     

Fatty Acid Desaturation and Elongation Reactions of <Emphasis Type="Italic">Trichoderma</Emphasis> sp. 1-OH-2-3

The fatty acid desaturation and elongation reactions catalyzed by Trichoderma sp. 1-OH-2-3 were investigated. This strain converted palmitic acid (16:0) mainly to stearic acid (18:0), and further to oleic acid (c9-18:1), linoleic acid (c9,c12-18:2), and α-linolenic acid (c9,c12,c15-18:3) through elongation, and Δ9, Δ12, and Δ15 desaturation reactions, respectively. Palmitoleic acid (c9-16:1) and cis-9,cis-12-hexadecadienoic acid were also produced from 16:0 by the strain. This strain converted n-tridecanoic acid (13:0) to cis-9-heptadecenoic acid and further to cis-9,cis-12-heptadecadienoic acid through elongation, and Δ9 and Δ12 desaturation reactions, respectively. trans-Vaccenic acid (t11-18:1) and trans-12-octadecenoic acid (t12-18:1) were desaturated by the strain through Δ9 desaturation. The products derived from t11-18:1 were identified as the conjugated linoleic acids (CLAs) of cis-9,trans-11-octadecadienoic acid and trans-9,trans-11-octadecadienoic acid. The product derived from t12-18:1 was identified as cis-9,trans-12-octadecadienoic acid. cis-6,cis-9-Octadecadienoic acid was desaturated to cis-6,cis-9,cis-12-octadecatrienoic acid by this strain through Δ12 desaturation. The broad substrate specificity of the elongation, and Δ9 and Δ12 desaturation reactions of the strain is useful for fatty acid biotransformation.     

Roquefortine/Oxaline Biosynthesis Pathway Metabolites in <Emphasis Type="Italic">Penicillium</Emphasis> ser. <Emphasis Type="Italic">Corymbifera</Emphasis>: <Emphasis Type="Italic">In Planta</Emphasis> Production and Implications for Competitive Fitness

Three strains of each of the seven taxa comprising the Penicillium series Corymbifera were surveyed by direct injection mass spectrometry (MS) and liquid chromatography–MS for the production of terrestric acid and roquefortine/oxaline biosynthesis pathway metabolites when cultured upon macerated tissue agars prepared from Allium cepa, Zingiber officinale, and Tulipa gesneriana, and on the defined medium Czapek yeast autolysate agar (CYA). A novel solid-phase extraction methodology was applied for the rapid purification of roquefortine metabolites from a complex matrix. Penicillium hordei and P. venetum produced roquefortine D and C, whereas P. hirsutum produced roquefortine D and C and glandicolines A and B. P. albocoremium, P. allii, and P. radicicola carried the pathway through to meleagrin, producing roquefortine D and C, glandicolines A and B, and meleagrin. P. tulipae produced all previously mentioned metabolites yet carried the pathway through to an end product recognized as epi-neoxaline, prompting the proposal of a roquefortine/epi-neoxaline biogenesis pathway. Terrestric acid production was stimulated by all Corymbifera strains on plant-derived media compared to CYA controls. In planta, production of terrestric acid, roquefortine C, glandicolines A and B, meleagrin, epi-neoxaline, and several other species-related secondary metabolites were confirmed from A. cepa bulbs infected with Corymbifera strains. The deposition of roquefortine/oxaline pathway metabolites as an extracellular nitrogen reserve for uptake and metabolism into growing mycelia and the synergistic role of terrestric acid and other Corymbifera secondary metabolites in enhancing the competitive fitness of Corymbifera species in planta are proposed.     

(7<Emphasis Type="Italic">Z</Emphasis>,9<Emphasis Type="Italic">E</Emphasis>)-2-Methyl-7,9-Octadecadiene: A Sex Pheromone Component of <Emphasis Type="Italic">Lymantria Bantaizana</Emphasis>

Our objective was to identify the sex pheromone of Lymantria bantaizana (Lepidoptera: Lymantriidae) whose larvae feed exclusively on walnut, Juglans spp., in China, and Japan. Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone gland extracts revealed a single EAD-active component. Retention index calculations of this compound on four GC columns suggested that it was a methyl-branched octadecadiene with conjugated double bonds. In GC-EAD analyses of 2-methyloctadecenes, (Z)-2-methyl-7-octadecene and (E)-2-methyl-7-octadecene elicited the strongest antennal responses, suggesting that the double bond positions were at C7 and C9. In comparative GC-EAD analyses of pheromone gland extract and stereoselectively synthesized isomers (E,E; E,Z; Z,E; Z,Z) of 2-methyl-7,9-octadecadiene, the (E,Z)- and (Z,E)-isomer had retention times identical to that of the candidate pheromone, but only the latter isomer elicited strong EAD activity. Results of field experiments in Japan substantiated that (7Z,9E)-2-methyl-7,9-octadecadiene is the L. bantaizana sex pheromone, a compound previously unknown in the Lepidoptera. Detection surveys in North America for exotic Eurasian forest defoliators could include traps baited with the L. bantaizana pheromone.     

Monitoring of Fat Content,Free Fatty Acid and Fatty Acid Profile Including <Emphasis Type="Italic">trans</Emphasis> Fat in Pakistani Biscuits

The fat contents of 12 brands of biscuits were extracted and evaluated for free fatty acids (FFA) and their fatty acid composition (FAC). The oil content and FFA varied from 13.7 to 27.6% and 0.2 to 1.0%, respectively. The FAC was analyzed by gas chromatography–mass spectroscopy with particular emphasis on trans fatty acids (TFA). Total saturated, unsaturated, cis-monounsaturated and polyunsaturated fatty acids were determined in the range of 37.9–46.9, 53.0–62.0, 12.3–43.7 and 0.1–9.2%, respectively. The high amount of TFA was observed in all biscuit samples and varied from 9.3 to 34.9%. The quantity and quality of the lipid fraction of the biscuits indicated that the all analyzed biscuits are a rich source of fat, saturated fatty acids and trans fatty acids, consequently not suitable for the health of consumers. The high content of trans fatty acids and palmitic acid also indicated that blends of RBD palm oil and partially hydrogenated oil had been used in the biscuit manufacturing.     

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.     

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.     

Reaction selectivity of <Emphasis Type="Italic">Burkholderia cepacia</Emphasis> (PS-30) lipase as influenced by monoacylation of <Emphasis Type="Italic">sn</Emphasis>-glycerol

Reaction selectivities were determined in multicompetitive reactions mediated by Burkholderia cepacia lipase (Amano PS-30) at a water activity of 0.19 in hexane. Saturated FA (C4–C18 even chain) and oleic acid (C18∶1) were reacted with a single alcohol, glycerol, α-or β-MAG, containing C4, C10, C16, or C18∶1 individually as alcohol cosubstrate. Similar odrinal patterns of FA selectivity, with C8, C10, and C16 preferred over others, were generally observed for incorporation of FA into specific acylglycerol (AG) pools of the 24 specific cases evaluated. The three exceptions were enrichment of C14 and C18 in the MAG pool with α-C16-MAG, substrate, and a general suppression of >C8 incorporation into the TAG pool for reactions with α-C10- and α-C16-MAG. PS-30 lipase selectivity toward MAG was in descending order: α/β-C4-MAG>β-C10-MAG>β-C16-MAG>α/β-C18∶1-MAG>α-C10-MAG>α-C16-MAG. Selectivity in channeling CX of the original CX-MAG substrates into higher AG species was in descending order: α-C10-MAG∼α-C16-MAG>α-C18∶1-MAG>β-C10-MAG∼β-C16-MAG∼β-C18∶1-MAG >α/β-C4-MAG. Generally, MAG were better acyl donors than FA for esterification reactions leading to DAG formation. These observations are relevant to the design of biocatalytic processes intended to yield specifically structured TAG.     

Phytotoxic and Antifungal Compounds from Two <Emphasis Type="Italic">Apiaceae</Emphasis> Species, <Emphasis Type="Italic">Lomatium californicum</Emphasis> and <Emphasis Type="Italic">Ligusticum hultenii</Emphasis>, Rich Sources of Z-ligustilide and Apiol,Respectively

The seeds of two Apiaceae species, Ligusticum hultenii and Lomatium californicum, were investigated. Preliminary bioassays indicated that methylene chloride extracts of seeds of both species contained selective phytotoxic activity against monocots and antifungal activity against Colletotrichum fragariae. Active constituents were isolated by bioassay-guided fractionation, and the structures were elucidated by NMR and GC-MS as apiol and Z-ligustilide, isolated from L. hultenii and L. californicum, respectively. Apiol and Z-ligustilide had I₅₀ values of about 80 and 600 μM, respectively, for inhibition of the growth of Lemna paucicostata. The methylene chloride (CH₂Cl₂) extracts of the seeds and the isolated and purified compounds were tested against the 2-methylisoborneol-producing cyanobacterium (blue-green alga) Oscillatoria perornata, and the green alga Selenastrum capricornutum. The CH₂Cl₂ extracts of both Apiaceae species and apiol were weakly toxic to both species of phytoplankton, while Z-ligustilide was toxic to both with a lowest complete inhibitory concentration (LCIC) of 53 μM. Seeds of L. californicum and L. hultenii were found to be rich sources of Z-ligustilide (97 mg/g of dry seed) and apiol (40 mg/g of dry seed), respectively.