Identification and preparation of antiinsectan dienols fromDipterocarpus kerrii tree resins

Originally isolated fromDipterocarpus kerrii, the two previously uncharacterized sesquiterpenes,1 and20, were synthesized from α-gurjunene. A novel process involvingm-chloroperoxybenzoic acid oxidation ofα-gurjunene produced20 in one step. Spectroscopic studies determined that the diene moiety in20 is nonconjugated and also found the C-4 tertiary alcohol center to have theα-configuration, while the other stereocenters have configurations matching the corresponding centers inα-gurjunene. Bioassays with termites demonstrated that20 was more toxic than1, resulting in a 50% mortality in seven days when offered toNeotermes ?dalbergiae on filter papers. The chemicals appear to result from biotransformation ofα-gurjunene. In view of its similarity to the known sesquiterpeneγ-gurjunene, we suggest that20 be referred to asγ-gurjunenol.     

Additional male mediterranean fruitfly (Ceratitis capitata wied.) Attractants from Angelica seed oil (Angelica archangelica L.)

Two sesquiterpene hydrocarbons, -copaene and -ylangene, were isolated from bioactive fractions of angelica seed oil and were shown by field bioassays to be attractive to the male Mediterranean fruit fly. Their relative attractiveness, compared with the(+)-and (–)--copaene enantiomers, are: (+)--copaene>angelica -copaene>angelica -ylangene>(–)--copaene. The enantiomer ratios for the two compounds are: -copaene, 61.4% (+), 38.6% (–); -ylangene, 91.9% (+), 8.1% (–).trans--Bergamotene was also isolated from the same fractions, but in sufficient quantity for bioassay [enantiomer ratio: 95.7% (+), 4.3% (–)].     

Selective synthesis of α-olefins on Fe-Zn Fischer-Tropsch catalysts

Fe/Zn oxides promoted with K and Cu selectively produce -olefins at typical Fischer-Tropsch synthesis conditions (2/1 H₂/CO, 1 MPa, and 270°C). The simultaneous presence of K and Cu introduces a synergistic activity enhancement while maintaining the high olefin selectivity obtained by alkali promotion. Structural and morphological differences in Fe-Zn oxides prepared from ammonium glycolate complexes or precipitated from nitrate solutions have only a small influence on catalytic properties. Catalyst behavior is strongly influenced by synergistic promoter effects (Cu, K) and by the controlled in situ conversion of iron oxide precursors to carbides.     

Inhibition of Fungal Spore Germination by Nasutitermes: Evidence for a Possible Antiseptic Role of Soldier Defensive Secretions

The antifungal property of two of the principal components of the terpenoid frontal gland secretions of nasute termite soldiers was studied by incubating spore suspensions of the fungus Metarhizium anisopliae with -pinene and limonene singly or in combination at different concentrations. In vitro assays showed that these substances reduced spore germination through direct and indirect (vapor) contact. To determine if the frontal gland secretions protected termites from fungal infection in vivo, the effect of M. anisopliae on the time course of survival of Nasutitermes costalis and N. nigriceps was studied by exposing termites to either a 4.3 × 10⁷ spores/ml or a control sporeless suspension. The caste composition of experimental groups was manipulated to create mixed-caste subcolonies and monocaste groups. Relative to Coptotermes formosanus, a species that relies on the mechanical defenses of soldiers, N. costalis and N. nigriceps were less susceptible to fungal infection. Spore-exposed N. costalis and N. nigriceps termites had 1.2 times the hazard ratio of death of controls, while the hazard ratio of death of spore-exposed C. formosanus was 11.4 times that of controls. Although the lower susceptibility to infection in Nasutitermes may be explained in part by the antifungal properties of -pinene and limonene, group composition also played a major role in the survival of spore-exposed termites. Mixed-caste and soldier monocaste groups had 3.4 and 4.7 times the hazard ratio of death, respectively, relative to the worker monocaste treatment. These results suggest that although Nasutitermes terpenoid secretions may have antifungal properties, the caste composition of groups and the social interactions of termites also play a role in determining susceptibility to fungal infection.     

Chemistry and Defensive Efficacy of Secretion of Burrowing Bug (Sehirus cinctus cinctus)

Adult Sehirus cinctus cinctus emit a volatile secretion from their metathoracic scent glands when tactually stimulated. We identified the volatile components by gas chromatography, high-performance liquid chromatography, and mass spectrometry. The secretion of both sexes contained (1R)-(+)--pinene, (1S)-(–)--pinene, -myrcene, (R)-(+)-limonene, and -terpinolene. Two additional compounds were found in only female secretions: (E)-2-hexenyl acetate and (E)-2-octenal. We also tested the defensive capability of this insect by offering it to various predators. Anoles, starlings, and a killdeer rejected S. c. cinctus after an initial sampling. These findings suggest that the secretion plays a defensive role.     

Response of the European elm bark beetle,Scolytus multistriatus (Coleoptera: Scolytidae), to isomers and components of its pheromone

Laboratory bioassays (two methods) and field tests demonstrated synergistic action of the three components [(–)-4-methyl-3-heptanol (I); (–)-2,4-dimethyl-5-ethyl-6,8-dioxabicylo[3.2.1]octane (-multistriatin) (II); and (–)--cubebene (III)] of the pheromone bouquet ofScolytus multistriatus. Individually and in pairs the components were slightly attractive; I+II was clearly the most active doublet. Indirect evidence indicates that only one of the four enantiomers of I is active. Of the , , and isomers of II, only the is active. With the addition of compound I, slightly attractive extract from mated females became nearly as active as extract from virgin females.     

Defensive secretions of new zealand tenebrionids:

The defensive secretions of four species of the genusArtystona endemic to New Zealand differ from those of other tenebrionids in that they contain -pinene and limonene, as well as the more characteristic quinones and alkenes. Adults and larvae ofA. obscura, A. erichsoni, A. rugiceps, andArtystona sp. feed on the lichenParmotrema reticulatum (Taylor), but the terpenes are not sequestered from it. The defensive secretions of the four species show some interspecific variation.     

Antioxidants in grasshoppers: higher levels defend the midgut tissues of a polyphagous species than a graminivorous species

Polyphagous grasshoppers consume plants that contain markedly greater amounts of potentially prooxidant allelochemicals than the grasses eaten by graminivorous grasshoppers. Therefore, levels of antioxidant defenses maintained by these herbivores might be expected to differ in accordance with host plant ranges. Antioxidant levels were compared in midgut tissues and gut fluids of a polyphagous grasshopper, Melanoplus sanguinipes, and a graminivorous grasshopper, Aulocara ellioti. Glutathione concentrations in midgut tissues of M. sanguinipes (10.6 mM) are among the highest measured in animal tissues and are twice as high as those in A. ellioti. -Tocopherol levels are 126% higher in midgut tissues of M. sanguinipes than in those of A. ellioti, and remain at high levels when M. sanguinipes is reared on plants containing a wide range of -tocopherol concentrations. Ascorbate levels in M. sanguinipes midgut tissues are 27% higher than in those of A. ellioti, but vary depending on the host plant on which they are reared. Midgut fluids of both species contain elevated levels of glutathione, as well as large (millimolar) amounts of undetermined antioxidants that are produced in the insects. The consumption of tannic acid decreases ascorbate concentrations in midgut tisssues and gut fluids of A. ellioti but has no effect on ascorbate levels in M. sanguinipes. The results of this study provide the first measurements of antioxidants in grasshoppers and suggest that the maintenance of high levels of antioxidants in the midgut tissues of polyphagous grasshoppers might effectively protect them from oxidative stress.     

Monoterpene oviposition stimulants ofDioryctria amatella in volatiles from fusiform rust galls and second-year loblolly pine cones

Volatiles collected on Poropak Q from fusiform rust galls (Cronartium quercuum F. sp.fusiforme) of loblolly pine for 3 hr were better ovi-position stimulants forDioryctria amatella (Hulst) females than extracts of 8-hr collections. GLC analysis of these extracts showed no major differences in relative monoterpene composition, although 8-hr collections contained an unidentified compound not detected in the 3-hr collections. Comparison of volatiles from second-year loblolly pine cones with those from fusiform galls showed that both containeddl--pinene, (–)--pinene, myrcene, and (+)-limonene. Camphene was found in galls only, and relatively large quantities of -phellandrene were identified only from cones. The five major monoterpenes found in the two host substrates were tested in an oviposition bioassay. Eighteen trials using different combinations of these terpenes showed that the combination of -pinene, myrcene, and limonene was as attractive toD. amatella females as all other terpene combinations, including turpentine.Lepidoptera: Pyralidae.     

Synthesis and properties of aromatic polyesters and brominated polyesters derived from α,α′-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene

The interfacial polycondensation technique was used for the preparation of polyarylates and brominated polyarylates. Polyarylates and brominated polyarylates were prepared by mixing a solution of diacid chloride such as terephthaloyl chloride, isophthaloyl chloride, or their mixture in dichloromethane with an aqueous alkaline solution of ,-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene or ,-bis(4-hydroxy-3,5-dibromophenyl)-1,4(or 1,3)-diisopropylbenzene using triethylbenzylammonium chloride as the phase transfer agent. Moderate to high molecular weight polyarylates with _inh up to 1.27 dL/g were obtained, and most of them could be cast into tough and flexible films depending on the polymer composition. In general, polymers containing more 1,3-isomer or isophthaloyl chloride moieties gave transparent and flexible films and had lower glass transition temperatures and higher solubility. Although these polymers have two isopropylidene linkages in their repeating units, they still exhibit moderately high thermal stability and show no obvious weight loss before 400 °C. The introduction of bromine on the polymer backbone caused a decrease of inherent viscosity, crystallinity, and thermal stability of the polyarylates, while causing an increase in glass transition temperature and a great enhancement of fire retardancy.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Preparation and properties of <Emphasis Type="Italic">α</Emphasis>-phenylcinnamylideneacetylated poly(2-hydroxyethyl methacrylate)

A photosensitive polymer, -phenylcinnamylideneacetylated poly(2-hydroxyethyl methacrylate) (poly(HEMA)), was synthesized and characterized. Light irradiation upon the photosensitive poly(HEMA) film induced gel formation via dimerization between the pendent -phenylcinnamylideneacetylates of the polymer. The gel content of the crosslinked polymer increased with increasing irradiation time and reached 60% when irradiated for 30 minutes. Correspondingly, the water content decreased from 27% to 18% with irradiation time increasing from 0 to 30 minutes. The solute permeability of the -phenylcinnamylideneacetylated poly(HEMA) without irradiation is about the same as that of the poly(HEMA) film. The crosslinked -phenylcinnamylideneacetylated poly(HEMA) film prepared by light irradiation had much lower permeability as compared with the non-crosslinked film. More specifically, the photocrosslinked film had the permeability of 5.37 × 10^–7 cm/s, 1.32 × 10^–7 cm/s and 0.53 × 10^–7 cm/s for p-nitrophenol, tryptophan and flurbiprofen, respectively. This photosensitive -phenylcinnamylideneacetylated poly(HEMA) provides a new base material for fabricating poly(HEMA) hydrogel.     

Multichemical defense of plant bugHotea gambiae (westwood) (Heteroptera: Scutelleridae)

Chemical defense in larvae of the plant bugHotea gambiae has been investigated. Results of analyses (GC, GC-MS) on the secretions from the three dorsally situated larval abdominal defense (scent) glands are reported. The secretion from the first abdominal gland consists of a mixture of C₁₀ and C₁₅ isoprenoids: (C₁₀) -pinene, -pinene, limonene, -phellandrene; (C₁₅) -caryophyllene, caryophyllene oxide, -humulene, and (the major component) humulene epoxide II. The secretions from the second and third abdominal glands are similar mixtures consisting of (E)-2-decenal, (E)-4-oxohex-2-enal, andn-tridecane together with lesser amounts of (E)-2-hexenal,n-dodecane, and other materials. Isoprenoid defense is now known from four species of plant bugs (Heteroptera) associated with Malvaceae.     

Light-dependent toxicity of α-terthienyl and anthracene toward late embryonic stages ofRana pipiens

Alpha-terthienyl is toxic to late embryonic stages ofRana pipiens in the presence of sunlight. Neither -terthienyl alone in the dark nor a previously photolyzed solution of -terthienyl has comparable activity. The LC₅₀ was 0.11 ppm with 30 min of exposure and 0.018 ppm with 2 hr of exposure to sunlight. Anthracene, a representative example of polycyclic aromatic hydrocarbons widely distributed in the environment, also showed similar phototoxicity, with an LC₅₀ of 0.065 ppm after 30 min of exposure and 0.025 ppm after 5 hr.     

(Z,E)-α-farnesene: Major component of secretion from metathoracic scent gland of cotton seed bug,Oxycarenus hyalinipennis (Costa) (Heteroptera; Lygaeidae)

The isolation and identification of (Z,E)--farnesene[(3Z, 6E)-3,7,11-trimethyldodeca-1,3,6,10-tetraene] (III) as the major component of the secretion from the metathoracic scent gland of the cotton seed bug,Oxycarenus hyalinipennis, is reported. The compound was identified by a combination of [1H] NMR, [¹³C] NMR, UV, and mass spectral data and by comparison with a synthetic sample, prepared by dehydration of (E)-nerolidol. (Z,E)--Farnesene (III) has been recorded previously in insects (ants and termites), but this is the first report of its occurrence in a member of the Heteroptera. (E)2-Octenyl acetate (XIII) and 2-octenal (XIV) were identified as minor components of the secretion. In addition, three minor monoterpenoid and two other sesquiterpenoid components were detected and tentatively identified.     

Hydroformylation of olefins with water-soluble rhodium catalysts in the presence ofα-cyclodextrin

Hydroformylation of hex-1-ene using a water soluble rhodium catalyst HRh(CO)[PPh₂(m-C₆H₄SO₃Na)]₃ (HRh(CO)(TPPMS)₃) (I), gives lower yields when-cyclodextrin is added to the biphasic reaction system implying an interaction between the cyclodextrin and rhodium catalyst.     

Highly Efficient Platinum-Catalyzed Enantioselective Hydrogenation of Trifluoroacetoacetates in Acidic Solvents

The hydrogenation of methyl-, ethyl- and isopropyl-4,4,4-trifluoroacetoacetates to the corresponding chiral trifluoromethyl alcohols has been investigated over Pt/A1₂O₃ modified by O-methyl-cinchonidine. Up to 96% ee and 1850 h^-1 average TOF have been achieved in the synthesis of this important chiral building block. The special role of reaction medium and particularly the impact of water and acids on enantiodiscrimination are discussed.     

Alkylation of α-Methylnaphthalene with Long-Chain Olefins over Large-Pore Zeolites

The liquid-phase alkylation of -methylnaphthalene with long-chain olefins (C_11–12) has been investigated firstly in the presence of H-Y and H-Beta zeolites with different pore architectures. The H-Y zeolites exhibited outstanding catalytic performances. The influences of various reaction parameters like temperature, pressure, mole ratio of -methylnaphthalene to olefins (n _rea), solvent concentration, volume hour space velocity (VHSV) and time on stream on the reaction were studied in detail. Under the optimal reaction parameters, more than 90% conversion of olefins and 100% selectivity for the desired mono-alkyl methylnaphthalene were achieved.     

Synergistic interaction between potato glycoalkaloidsα-solanine andα-chaconine in relation to destabilization of cell membranes: Ecological implications

In studies of the lysis of rabbit erythrocytes, red beet cells, andPenicillium notatum protoplasts by the potato glycoalkaloids -solanine and -chaconine, the latter was consistently the more membrane-disruptive compound and erythrocytes the more susceptible cell type. A 11 mixture of solanine and chaconine produced pronounced synergistic effects in all three test systems. In beet cells, such effects were apparent from an early stage of treatment and persisted over a period of several hours. With erythrocytes and fungal protoplasts, the synergism was maximal with mixtures containing approximately 70% chaconine, whereas with beet cells it peaked at approximately 40% chaconine. Synergistic interactions between solanine and chaconine also occurred with regard to cholesterol binding in vitro, with a maximum response corresponding to the 50% mixture. The implications of these findings for the nature and efficacy of chemical defense systems in plants are discussed.     

A miscibility study of ternary blends of polystyrene,tetramethylbisphenol-A polycarbonate,and poly(2,6-dimethyl-1,4-phenylene oxide)

Phase behaviorof ternary blends of polystyrene (PS), tetramethylbisphenol-A polycarbonate (TMPC), and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at two different temperatures (i.e., 210 and 300 °C, respectively) was studied by means of differential scanning calorimetry. Miscibility of the ternary blends at either temperature was found restricted to limited compositions, in agreement with simulated spinodal curves based on published values of interaction parameters. The limited ability of PS, which is separately miscible with TMPC and PPO at 210 °C, to act as a common solvent for the immiscible TMPC/PPO pair at this temperature was explained in terms of the disparity in PS/TMPC and PS/PPO pair interactions (i.e., the 'X effect).