Engelmann Spruce Chemotypes in Colorado and their Effects on Symbiotic Fungi Associated with the North American Spruce Beetle

Conifer secondary metabolites play a key role in mechanisms of resistance to biotic disturbance, especially by bark beetles and beetle-associated microorganisms. Here, we describe variation in constitutive monoterpenes isolated from Engelmann spruce, Picea engelmannii, phloem across fourteen high-elevation populations in the Rocky Mountains of Colorado, and test interactions between phloem monoterpenes and an endophloedic symbiotic fungus, Leptographium abietinum, associated with the North American spruce beetle, Dendroctonus rufipennis. We consistently identified ten monoterpenes in Engelmann spruce phloem, and the trees in our samples could be classified into two geographically interspersed chemical phenotypes, or ‘chemotypes’: one in which α- and β-pinene were the most abundant monoterpenes, and one in which 3-carene was the most abundant monoterpene. Media amended with low concentrations of α-pinene, β-pinene, 3-carene, myrcene, and terpinolene stimulated growth of L. abietinum. Increasing monoterpene concentrations uniformly retarded fungal growth. Linalool completely suppressed fungal growth at all concentrations, while terpinolene completely suppressed growth at low and intermediate concentrations, indicating relatively high toxicity of these compounds. Tests with monoterpene blends representing the ‘average’ monoterpene composition of each chemotype indicated that representative chemotypes are equivalent in fungistatic activity, with chemotype blends being inhibitory even at low concentrations. Total constitutive monoterpene abundances in Engelmann spruce phloem ranged from 42 to 1796 μg/g. Induction of Engelmann spruce phloem monoterpenes in response to L. abietinum or other biotic agents has yet to be quantified, but is important for further understanding Engelmann spruce resistance to the D. rufipennis-L. abietinum complex.     

Both Gas Chromatography and an Electronic Nose Reflect Chemical Polymorphism of Juniper Shrubs Browsed or Avoided by Sheep

Chemical polymorphism may contribute to variation in browsing damage by mammalian herbivores. Earlier, we demonstrated that essential oil concentration in juniper, Juniperus communis, was negatively associated with herbivore browsing. The aim of the present study was to characterize the volatile chemical composition of browsed and non-browsed J. communis. By using either gas chromatography with flame ionization detection (GC-FID) or an electronic nose device, we could separate sheep-browsed or non-browsed juniper shrubs by their essential oil pattern and complex odor matrix. The main components of the essential oil from J. communis were monoterpenes. We distinguished three chemotypes, dominated either by α-pinene, sabinene, or δ-3-carene. Shrubs belonging to the α-pinene- or sabinene-dominated groups were browsed, whereas all individuals with the δ-3-carene chemotype were unused by the local herbivores. The electronic nose also separated the browsed and non-browsed shrubs indicating that their odor matrix could guide sheep browsing. Responses of sheep could integrate the post-ingestive effects of plant secondary metabolites with sensory experience that stems from odor–phytotoxin interactions. Chemotype diversity could increase the survival rate in the present population of J. communis as certain shrubs could benefit from relatively better chemical protection against the herbivores.     

Weak responses of pine sawfly larvae to high needle flavonoid concentrations in scots pine

Responses of sawfly larvae (Hymenoptera, Diprionidae) to the flavonoid taxifolin glucoside in their host plant were studied in a laboratory experiment. Larvae ofNeodiprion sertifer andDiprion pini were raised from egg hatch to cocoon spinning on two Scots pine (Pinus sylvestris) chemotypes, one without needle taxifolin glucoside (–) and the other containing 2–4% taxifolin glucoside (+). The (+) chemotype had somewhat lower concentrations of needle terpenoids (resin acids) than the (–) chemotype. Current-year needles had higher taxifolin glucoside concentrations than mature needles. There were no differences in survival or body size betweenN. sertifer larvae that fed on the (+) chemotype and those that fed on the (–) chemotype. FemaleD. pini larvae raised on (+) needles developed 6% more slowly than larvae fed (–) needles. The results from this study are contrary to earlier findings showing that flavonoid glucosides have strong negative effects on insect performance. Possible explanations for the different outcomes are discussed.     

Changes in Monoterpene Emission Rates of <Emphasis Type="Italic">Quercus ilex</Emphasis> Infested by Aphids Tended by Native or Invasive <Emphasis Type="Italic">Lasius</Emphasis> Ant Species

The emission of volatile organic compounds (VOCs) depends on temperature and light. Other factors such as insect herbivory also may modify VOC emission. In particular, aphid feeding promotes the release of new compounds and changes the composition of plant volatile blends. Given that some aphids are tended by ants, we investigated whether ants change the emission of VOCs indirectly through attendance on aphids. The effect of Lachnus roboris aphids and two different tending ant species on terpene emission rates of 4-year-old holm oak (Quercus ilex) saplings was investigated during a field experiment. There were five treatments: saplings alone (T1), saplings infested with L. roboris aphids (T2), saplings infested with aphids tended by the local ant Lasius grandis (T3), those tended by small colonies of the invasive ant Lasius neglectus (T4), and those tended by large colonies of the same invasive ant species (T5). The infestation by L. roboris elicited the emission of Δ³-carene and increased the emission of myrcene and γ-terpinene. Terpene emissions were modified depending on the tending ant species. Attendance by the local ant L. grandis increased α and β-pinene and sabinene. Attendance by the invasive ant L. neglectus only decreased significantly the emission of myrcene, one of the major compounds of the Q. ilex blend. Aphid abundance decreased with time for all treatments, but there was no difference in aphid abundance among treatments. Total terpene emission rates were not correlated with aphid abundance. These results highlight that aphids and tending ants may change terpene emission rates, depending on the ant species.     

Qualitative and quantitative variation in monoterpene co-occurrence and composition in the essential oil of Thymus vulgaris chemotypes

Thymus vulgaris has a chemical polymorphism with six different chemotypes that show marked spatial segregation in nature. Although some populations have a single chemotype in majority, many have two or three chemotypes. In this study we analyze the quantitative variation among T. vulgaris populations in the percentage of oil composed of the dominant monoterpene(s) for each chemotype. In general, phenolic chemotypes (thymol and carvacrol), which occur at the end of the biosynthetic chain, have a significantly lower proportion of their oil composed of their dominant monoterpene than nonphenolic chemotypes (geraniol, -terpineol, and linalool). This is due to the presence of high amounts of precursors (-terpinene and paracymene) in the oil of phenolic chemotypes. The essential oil of the nonphenolic thuyanol chemotype has four characteristic monoterpenes that together make up a lower proportion of the oil than the single dominant monoterpene of the other nonphenolic chemotypes. For all chemotypes, the percentage composition of the dominant monoterpene decreased significantly at sites where the chemotype is not the majority type. This decrease is correlated with a significant increase in either the proportion of the two precursors for the thymol chemotype or the monoterpenes characteristic of the other chemotypes at the site. The latter result suggests that a plant with dominant genes is responsible for the production of different monoterpenes can produce several molecules.     

Comparing the Variation of Needle and Wood Terpenoids in Scots Pine Provenances

We determined variation in both the concentration and composition of terpenoids in needles and wood within nine Scots pine (Pinus sylvestris) provenances. Seedlings of different provenances representing a 1200-km N–S transect from Estonia to northern Finland were cultivated in Suonenjoki nursery field, central Finland, for seven years. Growth of seedlings and the number of vertical resin ducts in wood were also determined. -Pinene and 3-carene were the major monoterpenes both in the needles and wood. The total monoterpene concentration was about five times higher in the needles than in the wood. A strong positive correlation was found between proportional quantities of several terpenes of the needles and wood, particularly for 3-carene, sabinene, and terpinolene. The needles contained both labdane-type and tricyclic resin acids, whereas the wood contained only tricyclic ones. The wood had a four times higher tricyclic resin acid concentration than the needles. The highest total monoterpene concentration in the needles and in the wood occurred in the most northern Muonio provenance and in the most southern Saaremaa provenance plants, respectively. The amount of high 3-carene genotype trees decreased among the northern provenances. The wood of the most northern Muonio provenance showed the lowest total resin acid concentration, but provenance did not affect total tricyclic resin acids in the needles. Korpilahti provenance trees from central Finland had the best growth in height. In addition, Korpilahti and Ruokolahti provenance trees showed largest radial growth of stem and smallest number of vertical resin ducts. The results suggest that especially the proportional quantity of 3-carene in the needles could be used in estimating the amount of this compound in the wood and vice versa.     

Gas‐ versus liquid‐phase α-pinene transformation over faujasite‐like zeolites and an amorphous silicoaluminate

The transformation of α-pinene was studied in both gas and liquid phase over a series of faujasite‐like zeolites having different framework composition. A comparison with an amorphous silicoaluminate having 13 wt% of Al₂O₃ (SA) was made. Camphene + limonene were the major products observed in liquid phase at 393 K at conversion levels lower than 90%. At 473 K, where the reaction in gas phase took place, limonene suffered an ulterior transformation mainly into terpinenes and terpinolenes and a faster deactivation of the zeolite catalysts as compared to the one in liquid phase was observed. This behaviour contrasts with the high stability shown by SA in gas phase. Over the wider pore system of SA undesired heavy products were formed in liquid phase at the expenses of the terpene isomers. However, in gas phase this ulterior transformation of monoterpenes was minimised. A maximum activity for the zeolite catalysts was observed when the number of Al^IV per unit cell reached about 17, a value where the population of Si(0Al) sites has been shown to reach the maximum. This revised version was published online in July 2006 with corrections to the Cover Date.     

Seasonal Variation of Chemical Composition and Antioxidant Activity of Essential Oil from <Emphasis Type="Italic">Pistacia atlantica</Emphasis> Desf. Leaves

The composition and antioxidant activities of Pistacia atlantica Desf. essential oil were investigated. Qualitative and quantitative differences in compositions and in antioxidant activities of male and female leaf essential oils were observed during the season. The essential oils obtained by hydrodistillation were analysed by GC and GC–MS. The oils were rich in monoterpenes hydrocarbons and oxygenated sesquiterpenes. The main components of male essential oil were α-pinene/α-thujene, spathulenol and bicyclogermacrene. The major component of female essential oil was δ-3-carene. The seasonal variation showed that most of the main components of the oils reached theirs highest values in September. The antioxidant activity of the oil was investigated in vitro using two assays: DPPH^· (2,2-di-phenyl-1-picrylhydrazyl) free radical-scavenging and FRAP (Ferric Reducing Antioxidant Power). The highest antioxidant capacity to scavenge free DPPH radicals was reached in the month of June for male oils and during the months of September–October for the female oils. The high reducing power for male oil was observed during the month of June and for the female oil it was in August. The female oil was more active than the male oil. The antioxidant capacity of the female oil was almost ten times higher than Ascorbic acid in the FRAP assay.     

Conifer seed oils: Distribution of Δ5 acids between α and β chains by13C nuclear magnetic resonance spectroscopy

Nine seed oils from three different conifer families, already examined by gas chromatography and known to contain diene, triene, and tetraene C₁₈ and C₂₀Δ5 acids, have been reexamined by high-resolution¹³C nuclear magnetic resonance spectroscopy. The Δ5 acids are apparent only in the α-chains. This location is independent of chainlength, double-bond number, and the species considered and is probably a general factor of conifer seed oils. The spectra confirm the presence of oleic, linoleic, α-linolenic, and of Δ5 acids and give quantitative information about (total) n-6, n-3, and Δ5 acids that is in accord with that obtained by gas chromatography.     

Sources of Variation in Concentration and Composition of Foliar Monoterpenes in Tamarack (Larix laricina) Seedlings: Roles of Nutrient Availability, Time of Season, and Plant Architecture

The effects of foliage class, time of season, and nutrient availability on monoterpene composition and concentration were evaluated. In the first experiment, we compared foliar monoterpenes of long shoots versus short shoots, which differ in age and origin, and differences due to nutrient availability and time of season. Both the concentrations and compositions of these monoterpenes were higher in the foliage of the long shoots. The only exceptions were the concentration of -3-carene and the composition of -pinene. Within a foliage class, the concentrations of seven monoterpenes and the percentages of five monoterpenes changed over the season. Of these, almost all declined, with the exceptions of -pinene and an unknown. Nutrient availability significantly affected the concentration or composition of some monoterpenes, but only to a slight extent. -Pinene and the unknown increased with nutrient availability, whereas -pinene and myrcene decreased. A more comprehensive analysis of four foliage classes on a separate cohort of trees showed that all monoterpenes, except sabinene and terpinolene, differed between foliage classes, but there were few general patterns. Overall, within-tree variation in tamarack monoterpenes related to foliage class and age appears more important than between-tree variation due to nutrient availability. These results suppport the view that products of mevalonic acid biosynthesis, such as terpenes, do not follow predictions of the carbon–nutrient balance and growth differentiation hypotheses. Our overall results show that individual hosts need to be considered as phytochemical mosaics when interpreting herbivore–plant interactions.     

NMR study of the role of isopropylsulfates in the two-step “conjunct oligomerization” of propylene and isopentane–propylene alkylation catalyzed by 95% sulfuric acid

“Conjunct oligomerization” of propylene or the isopentane–propylene alkylation catalyzed by an excess of 95% sulfuric acid was performed in two consecutive steps. First di-isopropylsulfate was prepared by interaction of sulfuric acid with propylene. The ester was then either decomposed at room temperature in the presence of the 5–10 molar excess of 95% acid or was used in the acid-catalyzed alkylation of isopentane. In situ ¹H and ¹³C NMR study of the reaction mixture of “conjunct oligomerization” indicated that the diester participates in two equilibria with sulfuric acid. The first one transforms the diester into a monoester. The second equilibrium corresponds to protonation of the monoester with an excess of sulfuric acid. This converts a minor fraction of the mono-alkylsulfate into isopropyl carbenium ions that are only weakly solvated with sulfuric acid: C₃H₇HSO₄ + H₂SO₄ ⇄ C₃H₇ ⁺ H₂SO₄ + HSO₄ ⁻. The subsequent reactions of alkyl carbenium ions with the non-protonated alkylsulfate result in final products of “conjunct oligomerization” while in the presence in the reaction mixture of isopentane, alkylation with the predominant formation of C₈ branched paraffins takes place. A very low yield of propane indicates a minor role of hydride transfer in alkylation. Another unexpected result is the absence in both reaction mixtures of propylene. These findings are in contradiction with the classical mechanism of isoparaffin–olefin alkylation by Schmerling. Therefore, an alternative mechanism of this reaction is suggested via a direct alkylation of isopentane with the mono-alkylsulfate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Response to Host Volatiles by Native and Introduced Populations of Dendroctonus valens (Coleoptera: Curculionidae, Scolytinae) in North America and China

Bark beetles (Coleoptera: Curculionidae, Scolytinae) have specialized feeding habits, and commonly colonize only one or a few closely related host genera in their geographical ranges. The red turpentine beetle, Dendroctonus valens LeConte, has a broad geographic distribution in North America and exploits volatile cues from a wide variety of pines in selecting hosts. Semiochemicals have been investigated for D. valens in North America and in its introduced range in China, yielding apparent regional differences in response to various host volatiles. Testing volatiles as attractants for D. valens in its native and introduced ranges provides an opportunity to determine whether geographic separation promotes local adaptation to host compounds and to explore potential behavioral divergence in native and introduced regions. Furthermore, understanding the chemical ecology of host selection facilitates development of semiochemicals for monitoring and controlling bark beetles, especially during the process of expansion into new geographic ranges. We investigated the responses of D. valens to various monoterpenes across a wide range of sites across North America and one site in China, and used the resulting information to develop an optimal lure for monitoring populations of D. valens throughout its Holarctic range. Semiochemicals were selected based on previous work with D. valens: (R)-(+)-α-pinene, (S)-(−)-α-pinene, (S)-(−)-β-pinene, (S)-(+)-3-carene, a commercially available lure [1:1:1 ratio of (R)-(+)-α-pinene:(S)-(−)-β-pinene:(S)-(+)-3-carene], and a blank control. At the release rates used, (+)-3-carene was the most attractive monoterpene tested throughout the native range in North America and introduced range in China, confirming results from Chinese studies. In addition to reporting a more effective lure for D. valens, we present a straightforward statistical procedure for analysis of insect trap count data yielding cells with zero counts, an outcome that is common but makes the estimation of the variance with a Generalized Linear Model unreliable because of the variability/mean count dependency.     

Authenticating Production Origin of Gilthead Sea Bream (<Emphasis Type="Italic">Sparus aurata)</Emphasis> by Chemical and Isotopic Fingerprinting

Recent EU legislation (EC/2065/2001) requires that fish products, of wild and farmed origin, must provide consumer information that describes geographical origin and production method. The aim of the present study was to establish methods that could reliably differentiate between wild and farmed European gilthead sea bream (Sparus aurata). The methods that were chosen were based on chemical and stable isotopic analysis of the readily accessible lipid fraction. This study examined fatty acid profiles by capillary gas chromatography and the isotopic composition of fish oil (δ¹³C, δ¹⁸O), phospholipid choline nitrogen (δ¹⁵N) and compound specific analysis of fatty acids (δ¹³C) by isotope ratio mass spectroscopy as parameters that could reliably discriminate samples of wild and farmed sea bream. The sample set comprised of 15 farmed and 15 wild gilthead sea bream (Sparus aurata), obtained from Greece and Spain, respectively. Discrimination was achieved using fatty acid compositions, with linoleic acid (18:2n-6), arachidonic acid (20:4n-6), stearic acid (18:0), vaccenic acid (18:1n-7) and docosapentaenoic acid (22:5n-3) providing the highest contributions for discrimination. Principle components analysis of the data set highlighted good discrimination between wild and farmed fish. Factor 1 and 2 accounted for >70% of the variation in the data. The variables contributing to this discrimination were: the fatty acids 14:0, 16:0, 18:0, 18:1n-9, 18:1n-7, 22:1n-11, 18:2n-6 and 22:5n-3; δ¹³C of the fatty acids 16:0, 18:0, 16:1n-7, 18:1n-9, 20:5n-3 and 22:6n-3; Bulk oil fraction δ¹³C; glycerol/choline fraction bulk δ¹³C; δ¹⁵N; % N; % lipid.     

Isomerization of α-pinene over dealuminated ferrierite-type zeolites

Isomerization of α-pinene was performed on a series of dealuminated ferrierite (FER)-type zeolites in liquid phase at 363 K using a batch reactor. The course of zeolite dealumination was followed in detail using ²⁹Si, ²⁷Al, ¹H MAS NMR, XRD, FTIR, and sorption of nitrogen. The ammonium form of FER was dealuminated with aqueous solutions of HCl. While retaining the crystallinity of the zeolite particles, the treatments removed up to 53% of the tetrahedrally coordinated aluminum atoms from the FER framework. According to ²⁹Si MAS NMR studies, the framework aluminum atoms located at the 10-membered rings in the main channels of FER (T_B sites) were depleted preferentially from their positions. Even relatively mild dealumination of FER led to an active catalyst containing both Brønsted and Lewis centers, yielding up to 97% conversion of α-pinene at 363 K, in contrast to the 72% observed for the parent hydrogen form. Such catalytic behavior was discussed in terms of the conversion of a reactant inside micropores of the zeolite catalyst, on Brønsted acid centers with enhanced strength located probably in the vicinity of Lewis sites. The selectivity toward camphene and limonene changed smoothly with the dealumination level; thus, a higher selectivity toward limonene was observed at the expense of camphene formation with increasing the n_Si/n_Al ratio of the catalysts. The selectivity toward camphene and limonene was close to 85% for all of the materials studied. The initial rates of α-pinene transformations over FER-type materials exceeded those observed for other catalytic systems, heteropoly acid/SiO₂ and H₂SO₄/ZrO₂. This study demonstrates the successful application of a medium-pore zeolite for the catalytic transformation of α-pinene in liquid phase.     

Isomerization of α-pinene,limonene, α-terpinene,and terpinolene on sulfated zirconia

Transformations of α-pinene, limonene, terpinolene, and α-terpinene were studied in liquid phase on sulfated zirconia having 15% H₂SO₄, with the aim of identifing the pathway of α-pinene isomerization. The principal products obtained in α-pinene isomerization were camphene, tricyclene, limonene, and terpinolene; the concentration maxima observed at 120°C and 180 min were 53, 6.1, 7.7, and 3.0%, respectively. The principal products formed in the limonene transformation after a 20-min reaction time were terpinolene, α-terpinene, and γ-terpinene; then the concentration of these products decreased. The terpinolene reaction yielded principally m-cymenene, whereas the α-terpinene transformation produced p-cymene. Studies of the initial rates of transformation of terpenes indicate a very high rate for α-pinene, intermediate for limonene and α-terpinene, and very low for terpinolene. The scheme proposed to interpret the results of the α-pinene isomerization reaction on sulfated zirconia is in agreement with reaction schemes proposed by A. Allahverdiev, S. Irandoust, and D. Y. Murzin (Isomerization of α-Pinene over Clinoptilolite.     

ΝΗ<Subscript>3</Subscript> decomposition in a proton conducting solid electrolyte cell

The reaction of NH₃ decomposition was studied on Ag in a proton conducting double chamber cell-reactor. The proton conductor was a strontia-ceria-ytterbia (SCY) perovskite of the form SrCe_0.95Yb_0.05O_3−α. The reaction was studied at 350–700 °C and atmospheric total pressure. The proton transference number (PTN) was calculated by simultaneous measurement of the imposed current and the proton flux and it was found to vary between 0.5 and 0.7. The effects of imposed current, temperature and inlet gas composition on the reaction rate and the PTN, were examined. Although the faradaic efficiency (Λ) remained near unity in all experiments, reaction rate enhancements (ρ) as high as 57 were achieved. An up to 90% decrease in the activation energy of the reaction was observed when protons were electrochemically “pumped” away from the catalyst.     

Volatile Profile Differences and the Associated Sirex noctilio Activity in Two Host Tree Species in the Northeastern United States

Sirex noctilio females are known to be attracted to stem sections of stressed pine trees for oviposition. The volatile profiles and attractiveness of Eastern white pine (Pinus strobus) and two chemotypes of Scots pine (P. sylvestris) were compared after stem injection with herbicide. In general, trap captures on herbicide-treated trees were higher than on controls. The high-carene chemotype of Scots pine captured the highest numbers of females, followed by the low-carene chemotype, and finally the Eastern white pine. Herbicide-treated trees of both species emitted larger quantities of volatiles than the controls. The herbicide treatment induced higher volatile emission rates in the Scots pine chemotypes than in white pine, although there was no difference between the two chemotypes. However, qualitative differences were found between the volatile profiles of the two species as well as between the two Scots pine chemotypes, which could account for the differential attractiveness of the species and chemotypes tested.     

Seed oil fatty acids of loasaceae—A new source of γ-linolenic and stearidonic acids

The pharmaceutically interesting Δ6-FA 18∶3Δ6c, 9c, 12c (γ-linolenic acid) and 18∶4Δ6c,9c,12c,15c (stearidonic acid) appear to have evolved independently several times during plant phylogenetic evolution. They typically occur in “clusters” of a few closely related species or genera in about a dozen different plant families throughout the plant kingdom. A hither-unknown “cluster of occurrence” has now been discovered in the New World plant family Loasaceae. γ-Linolenic and stearidonic acids occur exclusively in representatives of the newly described genus Nasa at significance levels of between 3 and 10% each. Nasa had recently been separated from the older, more broadly circumscribed genus Loasa. The two Δ6-FA were not found in the closely related genus Loasa sensu stricto, nor in a number of other representatives of Loasaceae.     

Effects of nitrogen fertilization on secondary chemistry and ectomycorrhizal state of Scots pine seedlings and on growth of grey pine aphid

Effects of nitrogen availability on secondary compounds, mycorrhizal infection, and aphid growth of 1-year-old Scots pine (Pinus sylvestris L.) seedlings were studied during one growing season. Seedlings were fertilized with nutrient solutions containing low, optimum, and two elevated (2 × and 4 × optimum) levels of NH₄NO₃. At the end of growing season foliar nitrogen concentration, needle biomass, needle length, water contents of needles, root collar diameter, and number of buds increased with enhanced nitrogen availability. Addition of nitrogen did not have effect on concentrations of monoterpenes in growing needles, but in mature needles significantly decreased concentrations of some individual and total monoterpenes were detected. In growing needles the concentrations of some individual resin acids decreased, and in mature needles concentrations of some individual and total resin acids increased with increased nitrogen fertilization. Higher numbers of resin ducts were found in mature needles with nitrogen fertilization. Nitrogen fertilization decreased total phenolic concentrations in growing and mature needles of the current year, but in needles of the previous year no significant differences occurred. Mycorrhizal infection was highest at medium (optimum and 2 × optimum) nitrogen fertilization levels. The relative growth rate (RGR) of grey pine aphid [Schizolachnus pineti (F.)] responded positively to the increase in foliar nitrogen content. However, the increase in aphid performance between optimum and the highest fertilization level was slight. This may indicate a deterring effect of resin acids on aphids. The results indicate that carbon/nutrient balance hypothesis fails to predict directly the effects of nitrogen availability on concentrations of carbon-based defensive compounds in mature foliage. Altered nitrogen supply affects allocation to secondary metabolites differently, depending on the developmental state of the plant and the biosynthesis pathway, cost of synthesis, and storage of compounds.     

Synthesis and study of the surface properties of long-chain alkylnaphthalene sulfonates

Long-chain alkylnaphthalene sulfonates were synthesized by means of a Wurtz-Fittig reaction, and the basic properties were studied in water at 30°C. Through surface tension measurements, the following values were determined: the critical micelle concentration (CMC) and the surface tension at the CMC (γ_CMC). The following values were calculated: area per molecule at the CMC (A_CMC), standard free energy change of micellization (ΔG _mic ^o ), standard free energy of adsorption (ΔG _ad ^o ), and the “efficiency” of a surfactant in reducing surface tension (pC₂₀). The micelle aggregation numbers were measured through steady-state fluorescence-quenching methods. As the chain length of the hydrocarbon of n-alkylnaphthalene sulfonate increased, the Krafft temperature increased, the surface tension decreased, the value of CMC decreased, pC₂₀ increased, ΔG _ad ^o and ΔG _mic ^o became more negative, and the micelle aggregation number increased. The results showed that sodium α-(n-decyl)naphthalene sulfonate (DNS) had a high pC₂₀, low Krafft temperature, and lower CMC than other surfactants in this study. Thus, DNS and the other n-alkylnaphthalene surfactants studied exhibit desirable properties that may be of value in some fields such as detergency, oil recovery, and dyes.