Jean H. Langenheim

Higher plant terpenoids: A phytocentric overview of their ecological roles.

Characteristics of higher plant terpenoids that result in mediation of numerous kinds of ecological interactions are discussed as a framework for this Symposium on Chemical Ecology of Terpenoids. However, the role of terpenoid mixtures, either constitutive or induced, their intraspecific qualitative and quantitative compositional variation, and their dosage-dependent effects are emphasized in subsequent discussions. It is suggested that little previous attention to these characteristics may have contributed to terpenoids having been misrepresented in some chemical defense theories. Selected phytocentric examples of terpenoid interactions are presented: (1) defense against generalist and specialist insect and mammalian herbivores, (2) defense against insect-vectored fungi and potentially pathogenic endophytic fungi, (3) attraction of entomophages and pollinators, (4) allelopathic effects that inhibit seed germination and soil bacteria, and (5) interaction with reactive troposphere gases. The results are integrated by discussing how these terpenoids may be contributing factors in determining some properties of terrestrial plant communities and ecosystems. A terrestrial phytocentric approach is necessitated due to the magnitude and scope of terpenoid interactions. This presentation has a more broadly based ecological perspective than the several excellent recent reviews of the ecological chemistry of terpenoids.

Variation in terpenes and phenolics through leaf development in Hymenaea and its possible significance to herbivory

Abstract Leaf sesquiterpene resins and phenolic compounds were studied through leaf development in young greenhouse-grown plants of the tropical legume Hymenaea . Sesquiterpene composition and total yield were examined in seedlings and saplings of four resin Compositional Types . Terpene yield (mg resin/g dry wt leaf) was highest early in leaf development in all four types; composition changed significantly in only one type. Total phenolics and condensed tannins (% dry wt), and relative astrigency were highest in the leaf bud and decreased to low levels in leaf development. These results are discussed in relation to previous experiments which showed dose-dependent differential effects of three compositional types of Hymenaea defense theory.

Inhibitory effects of different quantitative compositions of Hymenaea leaf resins on a generalist herbivore Spodoptera exigua

Abstract The hypotheses that quantitative variation in leaf resins in the leguminous genus Hymenaea may partially be a response to insect predation was tested in feeding experiments with the generalist herbivore, the beet armyworm, Spodoptera exigua Hubn (Noctuidae). Leaf resins of all Hymenaea species are comprised of essentially the same suite of sesquiterpene hydrocarbons, but discrete quantitative patterns have been classified as Compositional Types based on the amounts of major components. In this work pure extracts of leaf resins of Type I (high α- and β-selinene), Type II (intermediate amounts of α-and β-selinene and caryophyllene) and Type III (high caryophyllene) were incorporated into an artificial diet for the insects at 1 and 3.2% (dry wt). Resin Type treatments produced differential dose-dependent effects on growth rate (lower larval weights and increased time to pupation) and in mortality. More significant inhibitory effects occurred in Compositional Types with a predominance of a single compared (i.e. Types I and III ). Significantly higher mortality occurring in Type III treatments suggests that caryophllene may have higher potential toxicity than α- and β-selinene for S. exigua . These experiments indicate that feeding by generalist herbivores could be a factor determining quantitative compositional variation: (a) among populations; (b) during the development of leaves; (c) in the spatial distribution within the leaves; and (d) between parent tree and seedling progeny.

Effect of light and temperature on monoterpenoid yield and composition in Satureja douglasii

Abstract Light intensity and day temperature were identified as principal modifying factors of monoterpenoid composition and yield in individuals of Satureja douglasii . The individuals represent compositional type and clinial patterns of infraspecific compositional variation. The lack of compositional interconversion confirms the tight genetic control of biosynthesis which results in these infraspecific patterns. There was marked influence by light intensity on monoterpenoid yield per leaf dry weight and by day temperature on yield per leaf. Low light intensity reduced leaf dry weight but had little effect on the amount of monoterpenoids per leaf whereas low day temperature increased both leaf weight and yield per leaf, compared to high light and day temperature effects. Day temperature modification of yield per leaf was related to modification of composition.

Implications of variation in resin composition among organs, tissues and populations in the tropical legume Hymenaea

Abstract Variation in leaf blade, petiole and primary stem resins, composed of sesquiterpene hydrocarbons, is analysed in two contrasting species of the tropical legume Hymenaea . Five populations of the New World H. courbaril , spanning a wide range of ecosystems, are compared with a population of the disjunct African H. verrucosa . Resins in petiole and primary stem tissue are similar, but differ significantly in total composition from leaf blade tissues. The major components, caryophyllene, α- and β-selinene and β-copaene vary most significantly among the tissues, but all compounds vary at highly significant levels among populations. The variation patterns in resin composition among the leaf blade and petiole/primary stem tissues are put into a larger context of comparison with the primarily diterpenoid patterns in secondary stem and pod tissues. Although the comparatively minor quantitative differences in the sesquiterpene systems could be attributed solely to developmental and physiological differences among the tissues and populations, the total weight of accumulating evidence regarding quantitative variation and demonstrated toxic and deterrent properties of sesquiterpene resins to insect herbivores leads us to hypothesize a possible role of differential predator pressures.

Inhibition of Nitrosomonas europaea by monoterpenes from coastal redwood (Sequoia sempervirens) in whole-cell studies

Inhibition by allelochemicals, including monoterpenes, has been suggested as a factor in the extremely low nitrification rates observed in coastal redwood forests. Similarities between the molecular structure of known nitrification inhibitors and some conifer monoterpenes have been suggested as one reason for the inhibition of autotrophic nitrifiers by conifer monoterpenes. The effect of monolerpenes on nitrification rate and growth of Nitrosomonas europaea was examined in whole-cell pure culture experiments using the five most abundant monoterpenes in coastal redwood needles. These are (in order of decreasing concentration in the needles) limonene, α-pinenc, sabinene, myrcene, and γ-terpinene. Four of the five compounds significantly inhibited growth of N. europaea in batch culture experiments. Short-term kinetic studies of the two most inhibitory monoterpenes, limonene and α-pinene, were performed on whole cells to evaluate the mode of interaction between these chemicals and nitrification rates. Inhibition constants (Ki) of limonene (38 μM) and α-pinene (95 μM) were determined. Lineweaver-Burk plots of nitrification in the presence of monoterpenes appear to fit a noncompetitive inhibition model; however, the mechanisms of inhibition may be more complex.

13C NMR and IR analyses of structure, aging and botanical origin of Dominican and Mexican ambers

Abstract 13 C NMR analysis of Oligocene amber from the Dominican Republic, Oligo-Miocene amber from Mexico and trunk resins from certain extant species of Hymenaea , suggests a polylabdane structure for all and gives insights into structural changes during aging. Additionally, IR spectra, some aspects of the 13 C NMR spectra and paleobotanical data suggest a close relationship between Dominican amber and H. verrucosa . By contrast, spectral evidence shows that Mexican amber differs, not only from the former polymers, but from the H. courbaril polymer.

Variation of Satureja douglasii monoterpenoids in relation to light intensity and herbivory

Abstract Genotypic variation of monoterpenoid yield and composition in Satureja douglasii was shown by growth of clonal transplants under uniform conditions. Differentiation of monoterpenoid yield was correlated with light intensity and degree of herbivory along transects. High-yielding genotypes occurred under low light, high herbivory conditions, whereas low-yielding genotypes occurred in high light, low herbivory conditions. Differentiation of monoterpenoid composition was more weakly correlated with herbivory and light intensity than was yield. There was also some evidence for seasonal variations of yield.

Effects ofHymenaea courbaril leaf resin on the generalist herbivoreSpodoptera exigua (beet armyworm)

The hypothesis that leaf resin ofHymenaea courbaril (Leguminosae) functions as a defence against herbivory was tested in a series of experiments with the generalist herbivore, beet armyworm (Spodoptera exigua Hübn). Pure leaf resin obtained by steam distillation was incorporated into an artificial diet at 0.0%, 0.16%, 0.50%, and 1.60% (dry weight) in one experiment and 0.0%, 1.0%, and 3.2% (dry weight) in a second experiment;S. exigua larvae were reared on these diets. In four palatability experiments the amount of leaf area eaten was compared between pairs of different leaf material. Mortality due to viral infection of larvae in the first feeding experiment showed a dose-response to leaf resin concentration. In the second experiment larvae showed a dose-response in the reduction of pupal weight and delay of time to pupation. These are interpreted as a dose-related stress onS. exigua which occurs with increased resin concentration in the diet. In the palatability tests,S. exigua strongly preferred untreated to resintreated bean leaf disks, bean disks toH. courbaril immature leaf disks,H. courbaril immature leaf toH. courbaril mature leaf, and bean leaf disks toH. courbaril newly emerged leaf disks. From these results, we conclude thatH. courbaril leaf resins possess toxic and feeding-deterrent properties which make them effective as an herbivore defense.

The effect of moisture stress on monoterpenoid yield and composition in Satureja douglasii

Abstract The effect of moisture stress on monoterpenoid yield and composition of Satureja douglasii was studied under controlled conditions and in the field. Large differences in monoterpenoid yield observed among field populations were closely correlated with moisture stress. In greenhouse transplants grown under uniformly moist conditions these differences were significantly reduced. In all plants studied yield per leaf dry weight decreased with development. A growth chamber study using clones grown under different soil moisture regimes showed that high moisture stress reduced leaf weight and monoterpenoid yield per leaf, but had little effect on yield per leaf dry weight. Effects on monoterpenoid composition were less striking with high moisture stress causing a small decrease in the percentage of monoterpenoids with a p -menthane carbon skeleton and perhaps accelerating the rate of developmental conversions.