Tannins in Puccinellia arctica: possible deterrents to herbivory by Canada geese.

Urban populations of Canada geese, Branta canadensis, pose a nuisance problem throughout most of the eastern United States and in other parts of the United States and Canada. Puccinellia arctica is a species of arctic grass that is unpalatable to Canada geese on the North Slope of Alaska and may prove to be an effective long-term and nonlethal means of controlling the growing populations of urban Canada geese. A comparative study of the secondary metabolites of both P. arctica and Puccinellia langeana and Poa pratensis, two palatable grass species that Canada geese generally consume, revealed no significant differences. However, ellagitannin levels were higher in P. arctica than in the palatable grass species and may be contributing to its unpalatability to Canada geese. These results support the potential to use P. arctica in public areas to control geese intrusions.

Two polyisoprenylated benzophenones from the trunk latex of Clusia grandiflora (Clusiaceae).

The polyisoprenylated benzophenones, chamones I and II, were isolated from the trunk latex of Clusia grandiflora (Clusiaceae) growing in southeastern Venezuela. A third benzophenone, nemorosone II, was isolated from the pollinator reward resin of the female flowers of the same plant. Chamone I and nemorosone II are structurally similar, differing only in the degree of prenylation. Bioassays of chamone I and nemorosone II using the honeybee pathogens, Paenibacillus larvae and Paenibacillus alvei, demonstrate that both have potent antibacterial activity, and that their structural differences affect both their bactericidal efficacies and their aqueous mobilities.

Salicortin: a repeat-attack new-mechanism-based Agrobacterium faecalis beta-glucosidase inhibitor.

Salicortin, a natural product abundant in most members of the Salicaceae family, is a mechanism-based inactivator of Agrobacterium faecalis beta-glucosidase. Inactivation is delayed in the presence of competitive inhibitors, thereby demonstrating the requirement for an enzyme-bound salicortin before inactivation. Product studies suggest that inactivation proceeds via a quinone methide intermediate formed by the fragmentation of the aglycone of salicortin while it is bound to the enzyme. Tryptic digest and HPLC/MS studies confirm the role of quinone methide attack and also show that the enzyme undergoes multiple modifications. In addition, when the inactivation was run in the presence of a mutant inactive form of the enzyme, HPLC/MS analyses clearly showed no modification of the mutant enzyme, demonstrating that the quinone methide does not exist in free solution and suggesting that inactivation is active-site directed.

Chemical defense ofPopulus balsamifera: A Clarification.

A previous report that the relative payabilities of juvenile versus maturePopulus balsamifera towards browsing snowshoe hares is due to the presence of 2,4,6-trihydroxydihydrochalcone in the juvenile growth form has been shown to be incorrect. Specifically, 2,4,6-trihydroxydihydrochalcone is present in internodes ofPopulus balsamifera in exceedingly low concentrations (<0.02% wet wt) and its concentrations are not elevated in internodes of the juvenile developmental stage. Its high levels in the buds (20-25% wet wt) ofPopulus balsamifera, however, probably makes it a deterrent substance for herbivores that cannot remove buds from twigs during foraging.

Carbon/nutrient balance as a predictor of plant defense in Alaskan balsam poplar: Potential importance of metabolite turnover.

The carbon/nutrient balance hypothesis fails to correctly predict effects of fertilization and shading on concentrations of defensive metabolites in Alaskan balsam poplar (Populus balsamifera). Of six metabolites analyzed, only one responded in the predicted fashion to fertilization and one to shading. These results and those of other similar studies suggest that while the carbon/nutrient balance hypothesis may correctly predict the effects of fertilization and shading on the concentrations of metabolic "end products", it fails for many metabolites because of the dynamics associated with their production and turnover. In metabolites that turn over, static concentration is a poor predictor of defensive investment.

Winter chemical defense of Alaskan balsam poplar against snowshoe hares.

Palatabilities of parts and growth stages of balsam poplar (Populus balsamifera) to snowshoe hares (Lepus americanus) are related to concentrations of specific plant metabolites that act as antifeedants. Buds are defended from hares by cineol, benzyl alcohol, and (+)-α-bisabolol. Internodes are defended by 6-hydroxycylohexenone (6-HCH) and salicaldehyde. Although defense of interaodes depends upon both compounds, the defense of juvenile internodes is principally related to salicaldehyde concentration; the defense of internode current annual growth is principally related to 6-HCH concentration. The concentration of 6-HCH can be supplemented by the hydrolysis of phenol glycosides when plant tissue is disrupted, raising the possibility of a dynamic element of the chemical defense of poplar.

Germacrone defends labrador tea from browsing by snowshoe hares.

Labrador tea (Ledum groenlandicum), a slow-growing late successional evergreen, is highly unpalatable to snowshoe hares (Lepus americanus). Germacrone, a sesquiterpene that is the major component of the essential oil ofL. groenlandicum, was shown by bioassay to be a potent antifeedant to hares. Its concentrations in leaves and intemodes of the plant are high enough to defendL. groenlandicum from hares. This chemical defense of Labrador tea from herbivory is consistent with the resource availability theory of antiherbivore defense.

Ecological implications of condensed tannin structure: A case study.

Condensed tannins were isolated from bitterbnish (Purshia tridentata) and blackbrush (Coleogyne ramosissima). Structural analyses showed that both tannins were procyanidins of similar polymer length. The overall stereochemistries at C-3 and C-4, however, differed between the two tannins. These changes in stereochemistry resulted in blackbrush tannins being less preferred than bitterbrush tannins when offered to snowshoe hares (Lepus americanus). It is unlikely that differences in protein-precipitating abilities are the cause for the preference of the bitterbrush over the blackbrush tannins. Instead, we hypothesize that condensed tannins may be depolymerized and absorbed following ingestion. Differences in tannin structure can lead to different depolymerized products and rates of depolymerization, both of which may affect herbivore preferences.

Ruffed grouse feeding behavior and its relationship to secondary metabolites of quaking aspen flower buds.

Quaking aspen (Populus tremuloides Michx.) staminate flower buds and the extended catkins are primary food resources for ruffed grouse (Bonasa umbellus). Winter feeding observations indicate that ruffed grouse select specific trees or clones of quaking aspen to feed in. Flower buds and catkins of quaking aspen were analyzed for secondary compounds (tannins, alkaloids, and phenolics) that might cause ruffed grouse to avoid trees with high levels of these compounds. Coniferyl benzoate, a compound that has not been previously found in quaking aspen, exists in significantly higher concentrations in buds from trees with no feeding history as compared to ruffed grouse feeding trees. Aspen catkins were also significantly lower in coniferyl benzoate than buds from the same tree. Ruffed grouse feeding preference was not related to the tannin or total phenolic levels found in buds or catkins. Buds from feeding trees had higher protein levels than trees with no feeding history; however, catkins did not differ from buds in protein concentration. The high use of extended catkins in the spring by ruffed grouse is probably due to a lower percentage of bud scale material in the catkin as opposed to the dormant bud. Bud scales contain almost all of the nontannin phenolics in catkins and dormant buds. A feeding strategy where bud scales are avoided may exist for other bird species that feed on quaking aspen. Dormant flower buds are significantly lower in protein-precipitable tannins than catkins and differ in secondary metabolite composition from other aspen foliage.

Chemical model for short-term induction in quaking aspen (Populus tremuloides) foliage against herbivores.

Simulated large aspen tortrix (Choristoneura conflictana) herbivory of quaking aspen (Populus tremuloides) induces significant increases in concentrations of two phenol glycosides, salicortin and tremulacin, in leaves within 24 hr. Crushing of leaf tissue, as must occur when aspen leaves are eaten by chewing insects such as the large aspen tortrix, results in conversion of salicortin and tremulacin to 6-hydroxy-2-cyclohexenone (6-HCH). Salicortin, tremulacin, 6-HCH, and its degradation product, catechol, are all toxic to the large aspen tortrix when fed on an artificial diet. These damage-induced chemical changes provide a plausible mechanism for short-term resistance induced in aspen leaves by insect herbivory.

Effect of nitrogen fertilization upon the secondary chemistry and nutritional value of quaking aspen (Populus tremuloides Michx.) leaves for the large aspen tortrix (Choristoneura conflictana (Walker)).

We investigated the effects of nitrogen fertilization upon the concentrations of nitrogen, condensed tannin and phenolic glycosides of young quaking aspen (Populus tremuloides) leaves and the quality of these leaves as food for larvae of the large aspen tortrix (Choristoneura conflictana), a Lepidopteran that periodically defoliates quaking aspen growing in North America. Nitrogen fertilization resulted in decreased concentrations of condensed tannin and phenolic glycosides in aspen leaves and an increase in their nitrogen concentration and value as food for the large aspen tortrix. These results indicate that plant carbon/nutrient balance influences the quality of aspen leaves as food for the large aspen tortrix in two ways, by increasing the concentrations of positive factors (e.g. nitrogen) and decreasing the concentrations of negative factors (eg. carbon-based secondary metabolites) in leaves. Addition of purified aspen leaf condensed tannin and a methanol extract of young aspen leaves that contained condensed tannin and phenolic glycosides to artificial diets at high and low levels of dietary nitrogen supported this hypothesis. Increasing dietary nitrogen increased larval growth whereas increasing the concentrations of condensed tannin and phenolic glycosides decreased growth. Additionally, the methanol extract prevented pupation. These results indicate that future studies of woody plant/insect defoliator interactions must consider plant carbon/nutrient balance as a potentially important control over the nutritional value of foliage for insect herbivores.

Response of winter chemical defense in Alaska paper birch and green alder to manipulation of plant carbon/nutrient balance.

Plant carbon/nutrient balance has been implicated as an important factor in plant defensive chemistry and palatability to herbivores. We tested this hypothesis by fertilizing juvenile growth form Alaska paper birch and green alder with N, P and N-plus-P in a balanced 2x2 factorial experiment. Additionally, we shaded unfertilized plants of both species. Fertilization with N and N-plus-P increased growth of Alaska paper birch, reduced the concentration of papyriferic acid in internodes and increased the palatability of birch twigs to snowshoe hares. Shading decreased birch growth, decreased the concentration of papyriferic acid in internodes and increased twig palatability. These results indicate that the defensive chemistry and palatability of winter-dormant juvenile Alaska paper birch are sensitive to soil fertility and shade. Conversely the defensive chemistry and palatability of green alder twigs to snowshoe hares were not significantly affected by soil fertility or shade. The greater sensitivity of Alaska paper birch defensive chemistry and palatability to snowshoe hares in comparison to green alder is in agreement with the hypothesis that early successional woody plants that are adapted to high resource availability are more plastic in their chemical responses to the physical environment than are species from less favorable environments.

Pinosylvin and pinosylvin methyl ether as feeding deterrents in green alder.

Snowshoe hare (Lepus americanus) feeding preferences for Alaskan green alder (Alnus crispa) are governed by the concentrations of two deterrent secondary metabolites, pinosylvin and pinosylvin methyl ether. For instance, the preference of mature internodes over juvenile internodes was correlated with about a threefold increase in the levels of these compounds in the juvenile form. During the last year of the study, however, the levels of these compounds dropped below the threshold of avoidance in both types of internodes, resulting in nondiscriminatory use by hares even though the relative levels of these metabolites remained the same between the juvenile and mature form internodes. These conclusions are strongly supported with feeding bioassays using pure pinosylvin, pinosylvin methyl ether, and other less active secondary metabolites found in alder.