Antifungal Activity of a New Phenolic Compound from Capitulum of a Head Rot-resistant Sunflower Genotype

In a previous study, we observed that bract and corolla extracts from a Sclerotinia sclerotiorum-resistant sunflower contained high amounts of the known coumarins scopoletin, scopolin, and ayapin. There was a correlation between coumarin concentration and disease resistance. Thin layer chromatography showed higher concentrations of three other compounds in the resistant genotype when compared to the susceptible. A bioassay-directed purification that used column chromatography and HPLC allowed the isolation of a new compound, 3-acetyl-4-acetoxyacetophenone, and known compounds, demethoxyencecalin and 3-acetyl-4-hydroxyacetophenone. Structures were assigned from spectral data, and bioactivities were characterized by in vitro bioassays against S. sclerotiorum. The new compound, 3-acetyl-4-acetoxyacetophenone, had an antifungal activity similar to the coumarin ayapin, previously described as a potent Sclerotinia inhibitor. The speed and simplicity by which these compounds can be detected make them suitable for use in screening procedures that may identify genotypes with valuable levels of resistance. A screening of seven sunflower genotypes in a field experiment showed a correlation between these compounds and resistance to Sclerotinia.     

Epidermal Lipoxygenase Products of the Hepoxilin Pathway Selectively Activate the Nuclear Receptor PPARα

Arachidonic acid can be transformed into a specific epoxyalcohol product via the sequential action of two epidermal lipoxygenases, 12R-LOX and eLOX3. Functional impairment of either lipoxygenase gene (ALOX12B or ALOXE3) results in ichthyosis, suggesting a role for the common epoxyalcohol product or its metabolites in the differentiation of normal human skin. Here we tested the ability of products derived from the epidermal LOX pathway to activate the peroxisome proliferator-activated receptors PPARα, γ, and δ, which have been implicated in epidermal differentiation. Using a dual luciferase reporter assay in PC3 cells, the 12R-LOX/eLOX3-derived epoxyalcohol, 8R-hydroxy-11R,12R-epoxyeicosa-5Z,9E,14Z-trienoic acid, activated PPARα with similar in potency to the known natural ligand, 8S-hydroxyeicosatetraenoic acid (8S-HETE) (both at 10 μM concentration). In contrast, the PPARγ and PPARδ receptor isoforms were not activated by the epoxyalcohol. Activation of PPARα was also observed using the trihydroxy hydrolysis products (trioxilins) of the unstable epoxyalcohol. Of the four trioxilins isolated and characterized, the highest activation was observed with the isomer that is also formed by enzymatic hydrolysis of the epoxyalcohol. Formation of a ligand for the nuclear receptor PPARα may be one possibility by which 12R-LOX and eLOX3 contribute to epidermal differentiation.     

Bidirectional Selection for Novel Pheromone Blend Ratios in the Almond Moth, <Emphasis Type="Italic">Cadra cautella</Emphasis>

The sex pheromone of the almond moth, Cadra cautella, is a blend of (Z,E)-9,12-tetradecadienyl acetate (Z9,E12–14:Ac, the major component capable of inducing attraction alone) and (Z)-9-tetradecenyl acetate (Z9–14:Ac, the minor component, which is unattractive alone but augments attraction of the major component). In this study, the ratio of the two components responded to artificial directional selection in five of six selected lines, whereas no change was observed in the three control lines. The mean ratio (±SE) of Z9,E12–14:Ac to Z9–14:Ac went from 13.72 ± 1.02:1 to 20.13 ± 0.68:1 in high line 1, an increase of 47%. In the second high-selected line, the mean ratio (±SE) increased from 9.87 ± 0.54:1 to 15.89 ± 0.85:1, an increase of 61%. In low line 1, the mean ratio (±SE) in the parental generation was 10.74 ± 0.78:1 and 7.35 ± 0.41:1 in the last selected generation, a decrease of 32%. The response to selection was greater in low line 2, as the mean ratio (±SE) decreased from 10.11 ± 0.66:1 to 5.65 ± 0.55:1 in the last generation, a decrease of 44%. In low line 3, the mean ratio (±SE) in the parental generation was 13.63 ± 0.82:1 and 6.47 ± 0.26:1 in the last generation, a decrease of 53%. The response to selection was approximately symmetrical with a mean increase of 54% and a mean decrease of 43%. The increases in ratio observed in the high lines were caused by an increase in the titer of the Z9,E12–14:Ac component with no concurrent change in the titer of the component Z9–14:Ac. Among the low selected lines, the titers of both components increased; however, there was a greater relative increase in the titer of the component Z9–14:Ac. The absolute and relative titers of the sex pheromone components had decreased significantly in the F10 generation in some of the selected lines, five generations after the discontinuation of selection.     

Jasmonate,Salicylate, and Benzoate in Insect Eggs

Jasmonic acid (JA) and salicylic acid (SA) are key molecules in the initiation of plant defensive responses to attack by herbivores and pathogens, respectively. Our previous work has shown that JA occurs at high concentrations in eggs and neonates of lepidopteran species. Here, we extend our analyses to eggs of 15 non-lepidopteran insect species spanning eight orders, again screening for JA, but also including SA and one of its metabolic precursors, benzoic acid. We detected all three compounds in eggs of almost all the species examined. Moreover, concentrations of these compounds were variable across species, suggesting that species accumulate and/or utilize the compounds differently. Eggs of the fruit-feeding fly Rhagoletis pomonella contained the greatest concentrations of all three compounds, which appear to be common in fruit. The presence of these plant-derived compounds in eggs may serve defensive or other functions for insects, and could conceivably trigger plant defensive responses after oviposition.     

Matching ratio between positive and negative electrodes for double-layer capacitors

For double-layer capacitors in alkaline electrolyte, the specific capacitance of the positive electrode is not equal to that of the negative one. Thus, capacitor performance cannot be optimal with a positive/negative electrode matching ratio of 1. In this study nanoporous glassy carbons (NPGCs) were employed as the electrodes of capacitors, and the influence of matching ratio between positive and negative electrode on capacitor performance was systematically investigated. In aqueous KOH, the specific capacitance of the positive electrode is lower than that of the negative electrode. The matching ratio at which a maximum capacitance is obtained is dependent on the values of the positive and negative electrode capacitance. At low current rate, the highest specific capacitance is achieved at a matching ratio slightly higher than 1. At high current rate, a capacitor has the highest specific capacitance with the lowest resistance at a matching ratio of 1.5. This indicates that an optimum matching relationship between positive and negative electrodes is attained.     

Modeling and economic analysis of CO<Subscript>2</Subscript> separation process with hollow fiber membrane modules

The main purpose of the study was to develop a model using ASPEN and Excel simulation method to establish optimum CO₂ separation process utilizing hollow fiber membrane modules to treat exhaust gas from LNG combustion. During the simulation, optimum conditions of each CO₂ separation scenario were determined while operating parameters of CO₂ separation process were varied. The characteristics of hollow fibers membrane were assigned as 60 GPU of permeability and 25 of selectivity for the simulation. The simulation results illustrated that 4 stage connection of membrane module is required in order to achieve over 99% of CO₂ purity and 90% of recovery rate. The resulted optimum design and operation parameters throughout the simulation were also correlated with the experimental data from the actual CO₂ separation facility which has a capacity of 1,000 Nm³/day located in the Korea Research Institute of Chemical Technology. Throughout the simulation, the operating parameters of minimum energy consumption were evaluated. Economic analysis of pilot scale of CO₂ separation plant was done with the comparison of energy cost of CO₂ recovery and equipment cost of the plant based on the simulation model. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Synthesis of Optically Active Dendrimers Having Chiral Bisphosphine as a Core

Summary First and second generation chiral dendrimers P-1G1, P-2G1, P-1G2 and P-2G2 containing chiral bisphosphine as a core were synthesized via a reaction of chiral bisphosphine compound (S,S)-1 with benzyl ether dendrons. This is the first example of chiral dendrimers containing chiral phosphorus atoms. To investigate the effect of chiral phosphorus atoms on their conformations, optically inactive dendrimer P′-2G1 was synthesized as well using optically inactive initiator 1′ which was the mixture of rac-1 ((S,S)-1 and (R,R)-1) and meso-1. Their structures were characterized by ¹H, ¹³C, ³¹P NMR, and HRMS. According to CD measurement, optically active dendrimers exhibited the Cotton effect induced by the chirality of phosphorus atoms, while optically inactive dendrimer P′-2G1 showed no Cotton effect.     

Purification of 2-mercaptobenzothiazole by solvent extraction

−Purification of 2-mercaptobenzothiazole (91.9% purity) by solvent extraction was studied. The extraction of impurities present in crude 2-MBT (e.g. benzothiazole, sulfides and sulfur containing compounds) was carried out at temperatures between 70-180°C using various solvents and their mixtures of different polarity. The highest purity of 2-MBT, above 99% was obtained using nitrobenzene, toluene and ethanol, even at a concentration of 2-MBT above 50 wt%. Increasing temperature and decreasing concentration of the raw material have a positive influence on the purification process. A comparable efficiency of purification was observed also with mixed solvents, (toluene with ethanol, acetone and aniline) possessing the same polarities. A correlation between the polarity indexes (PI) of mixed solvents and experimentally obtained purity of 2-MBT was found. The highest purity of 2-MBT provides extraction of the raw material with mixed solvents having PI 3.8-4.4.     

Root-secreted Allelochemical in the Noxious Weed <Emphasis Type="Italic">Phragmites Australis</Emphasis> Deploys a Reactive Oxygen Species Response and Microtubule Assembly Disruption to Execute Rhizotoxicity

Phragmites australis is considered the most invasive plant in marsh and wetland communities in the eastern United States. Although allelopathy has been considered as a possible displacing mechanism in P. australis, there has been minimal success in characterizing the responsible allelochemical. We tested the occurrence of root-derived allelopathy in the invasiveness of P. australis. To this end, root exudates of two P. australis genotypes, BB (native) and P38 (an exotic) were tested for phytotoxicity on different plant species. The treatment of the susceptible plants with P. australis root exudates resulted in acute rhizotoxicity. It is interesting to note that the root exudates of P38 were more effective in causing root death in susceptible plants compared to the native BB exudates. The active ingredient in the P. australis exudates was identified as 3,4,5-trihydroxybenzoic acid (gallic acid). We tested the phytotoxic efficacy of gallic acid on various plant systems, including the model plant Arabidopsis thaliana. Most tested plants succumbed to the gallic acid treatment with the exception of P. australis itself. Mechanistically, gallic acid treatment generated elevated levels of reactive oxygen species (ROS) in the treated plant roots. Furthermore, the triggered ROS mediated the disruption of the root architecture of the susceptible plants by damaging the microtubule assembly. The study also highlights the persistence of the exuded gallic acid in P. australis’s rhizosphere and its inhibitory effects against A. thaliana in the soil. In addition, gallic acid demonstrated an inhibitory effect on Spartina alterniflora, one of the salt marsh species it successfully invades. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Absorption Properties of Micellar Lipid Metabolites into Caco2 Cells

To elucidate the absorption characteristics of dietary lipids in the human intestine, we investigated the cellular uptake of lipid metabolites using a differential monolayer of the Caco2 cells. As lipid metabolites, several free fatty acids and 2-monoacylglycerols, were formed a mixed micelle by bile salts and lysophospholipids and they were supplied to the Caco2 cells. To estimate the effect of the mixed micelles on the permeability of cells’ membranes during incubation with the mixed micelles, the transepitherial electrical resistance (TEER) value was monitored, and no pronounced changes of TEER was detected. This suggested that mixed micelles did not affect their cellular properties of the barrier measured by TEER. The lipid metabolites transferred from the mixed micelle into the Caco2 cells were determined quantitatively by an enzymatic colorimetric method and were done by thin layer chromatography (TLC) for a species of acylglycerols. These highly sensitive methods enabled us to monitor the transepithelial transports of various kinds of non-isotope-labeled various lipid metabolites. Newly re-synthesized triacylglycerols were accumulated in Caco2 cells after 30 min incubation with the mixed micelles, and their amounts increased gradually for 4 h. The secretion of re-esterified triacylglycerols into a basolateral medium from the Caco2 cells began at 2 h after the mixed micelles were added to the apical medium. The intake of external lipid metabolites by the Caco2 cells were evaluated by an initial 2-h incubation with the mixed micelles. For example, 2-monomyristin and 2-monopalmitin were more rapidly transferred into the Caco2 cells from the mixed micelles than 2-monocaprin was. On the other hand, the absorption rates of capric acid, lauric acid and myristic acid by the cells were larger than those of stearic acid and oleic acid. It revealed that the side-chain structure of these lipid metabolites affected their absorption by the Caco2 cells. The results of this study suggested that the Caco2 cell monolayer could be a useful model for investigating the involvement of dietary lipids in the transepithelial absorption in the human intestine.