Impact of Plant Phenolics as Semiochemicals on the Performance of <Emphasis Type="Italic">Trichogramma chilonis</Emphasis> Ishii

Phenolic compounds play a major role in the plant defense mechanisms and often offer protection from the feeding herbivore. They also constitute a major chemical component of many agriculturally important crops. We examined the effects of 23 common phenolic acids on the orientation and ovipositional behavior of the egg parasitoid, Trichogramma chilonis Ishii (Hymenoptera: Trichogrammatidae). The study was conducted in order to investigate the function of these compounds in the plant indirect defense. Parasitoids attractions towards the phenolics that are volatile in nature were observed by using culture tube bioassays. In addition in the Y- tube olfactometer experiments, T. chilonis were shown to be attracted towards the treatments of syringic, pyrocatechol, coumaric and quercetin at minimum dose of 10 μg and genistein, chlorogenic, vanillic, chlorobenzoic, sinapic, ellagic, protocatechuic, keampferol, tannic, caffeic, and luteolin at 30 μg and ferulic, epicatechin and gallic acid at 50 μg doses. Further experiments to examine the effect of phenolic compounds on parasitization by T. chilonis females were carried out using petri dish and artificial plant models. Among the tested compounds, syringic acid and quercetin recorded the highest percentage parasitization followed by coumaric acid and pyrocatechol. These results might imply that parasitoid attractant phenolic compounds when induced in engineered plants can further be used as cues by the egg parasitoids with potential application in biocontrol strategies.     

Induction of phenolic acids and metals in Arachis hypogaea L. plants due to feeding of three lepidopteran pests

The feeding of lepidopteran pests, Amsacta albistriga W., Aproaerema modicella D. and Spilosoma obliqua W., caused feeding stress in the Arachis hypogaea L. plants. As a common defensive response, the plant exhibited variations in the primary and secondary metabolic contents. Groundnut plant antioxidative enzymes such as peroxidase, superoxide dismutase, polyphenol oxidase, catalase and phenyl ammonia lyase exhibited alterations to confer resistance against the pest. Phenolic compounds, namely coumaric acid, chlorogenic acid, resveratrol, epicatechin, ferulic acid and caffeic acid, showed active defensive role in groundnut plant against the pest feeding through their significant presence in Fourier transform infrared spectroscopy, high-performance liquid chromatography and gas chromatography studies. Changes in metal contents like iron, magnesium, zinc, potassium and calcium were also reported through atomic absorption studies, indicating their defensive role against the biotic stress caused on groundnut by the three lepidopteran pests. The present study can further assist in recognizing the importance of these specific phenolic acids and metals of groundnut in its pest management.     

Role of castor plant phenolics on performance of its two herbivores and their impact on egg parasitoid behaviour

Plants are reported to reconfigure their metabolism and generate secondary metabolites as a defence response towards herbivore attack. In this study we aimed to evaluate the anti-nutritive and defensive properties of phenolic compounds that were enhanced in Castor, Ricinus communis L. plant due to herbivore damage. Through HPLC studies it was observed that damage caused by two pests, Achaea janata L. and Spodoptera litura F. on the castor plant resulted in quantitative enhancement of syringic, coumaric, cinnamic and vanillic acids. These phenolic compounds showed considerable impact on insect’s feeding and their toxic nature towards the herbivores was determined by estimating three detoxification mid-gut enzymes, glutathione-s-transferase, carboxyl esterase and β-glucosidase. In the ovipositional and orientation bioassays with the egg parasitoid Trichogramma chilonis Ishii, syringic and coumaric acids had shown good kairomonal activity, thus defining a new role of these chemicals in indirect plant defence. Thus, this study demonstrates a quantitative association between plant phenolic accumulation and the elevated reproductive performance of the herbivore natural enemies, by illustrating the role of plant phenolics in both the direct and indirect induced plant defences.     

Changes in Cell Wall-bound Phenolic Compounds and Lignin in Roots of Date Palm Cultivars Differing in Susceptibility to Fusarium oxysporum f. sp. albedinis

The roots of date palm contain four cell wall‐bound phenolic acids identified as p‐hydroxybenzoic, p‐coumaric, ferulic and sinapic acids. The ferulic acid represents the major phenolic compound since it constitutes 48.2–55.8% of cell wall‐bound phenolic acids. All these phenolic acids were present in the resistant cultivar (BSTN) and the susceptible cultivar (JHL). However, the pre‐infection contents of p‐coumaric, ferulic and sinapic acids were greater in the resistant cultivar than in the susceptible one. For the contents of p‐hydroxybenzoic acid, there was no significant difference between the resistant cultivar and the susceptible cultivar. Similarly, the pre‐infection contents of lignin were approximately equal for both cultivars. Inoculation of the date palm roots by Fusarium oxysporum f. sp. albedinis induced important modifications to the contents of the cell wall‐bound phenolic compounds and lignin, which made it possible to distinguish between resistant and susceptible cultivars. The post‐infection contents of cell wall‐bound phenolic compounds underwent a rapid and intense increase with a maximum accumulation on the tenth day for p‐hydroxybenzoic acid (1.54 μmol/g), p‐coumaric acid (2.77 μmol/g) and ferulic acid (2.64 μmol/g) and on the fifteenth day for sinapic acid (1.85 μmol/g). The maximum contents accumulated in the resistant cultivar were greater than those in the susceptible cultivar, namely, 11 times for p‐hydroxybenzoic acid, 2.6 times for p‐coumaric acid, 1.8 times for ferulic acid and 12.3 times for sinapic acid. In the susceptible cultivar, p‐coumaric acid and ferulic acid contents also increased after inoculation although they did not reach the pre‐infection contents of the resistant cultivar. The contents of p‐hydroxybenzoic acid in the susceptible cultivar roots did not present post‐infection modification and those of sinapic acid decreased instead. The lignin contents increased in both cultivars with a maximum accumulation on the fifteenth day. However, the maximum contents accumulated in the resistant cultivar roots were 1.5 times greater than those of the susceptible cultivar. These results showed clear differences between the resistant BSTN and the susceptible JHL cultivars. The implication of cell wall‐bound phenolic compounds and lignin in the resistance of date palm to F. oxysporum f. sp. albedinis appears to be dependent on the speed and intensity of their accumulation with greater contents in the first stage of infection.     

Response of Lactobacillus casei BL23 to phenolic compounds

Aims: To determine the inhibitory effect of phenolic compounds on Lactobacillus casei BL23, the role of two component signal transduction systems (TCS) and the response of Lact. casei BL23 to p‐coumaric acid. Methods and Results: Growth of Lact. casei BL23 and 17 derivative strains defective in each TCS harboured by this strain in the presence of p‐coumaric acid, ferulic acid, caffeic acid or methyl gallate was monitored. Furthermore, changes in the protein content of Lact. casei BL23 when exposed to p‐coumaric acid were evaluated by 2D‐SDS‐PAGE. Eleven proteins differentially expressed in the presence of p‐coumaric acid were detected. Six of them could be identified: ClpP and HtrA, involved in protein turnover and folding, acetyl‐CoA carboxylase, involved in lipid metabolism, and an arginyl‐tRNA synthetase were more abundant, whereas PurL and PurN, involved in purine biosynthesis, were less abundant. Conclusions: No significant differences were observed between the parental strain and the TCS‐defective mutants. p‐Coumaric acid elicited a response against membrane and cytoplasmic damages. Significance and Impact of the Study: The inhibitory effect of phenolic compounds on Lact. casei BL23 has been determined. For the first time, cytoplasmic proteins presumably involved in the response of Lact. casei BL23 against p‐coumaric acid have been identified.     

Wine phenolic compounds influence the production of volatile phenols by wine-related lactic acid bacteria

Aims: To evaluate the effect of wine phenolic compounds on the production of volatile phenols (4‐vinylphenol [4VP] and 4‐ethylphenol [4EP]) from the metabolism of p‐coumaric acid by lactic acid bacteria (LAB). Methods and Results: Lactobacillus plantarum, Lactobacillus collinoides and Pediococcus pentosaceus were grown in MRS medium supplemented with p‐coumaric acid, in the presence of different phenolic compounds: nonflavonoids (hydroxycinnamic and benzoic acids) and flavonoids (flavonols and flavanols). The inducibility of the enzymes involved in the p‐coumaric acid metabolism was studied in resting cells. The hydroxycinnamic acids tested stimulated the capacity of LAB to synthesize volatile phenols. Growth in the presence of hydroxycinnamic acids, especially caffeic acid, induced the production of 4VP by resting cells. The hydroxybenzoic acids did not significantly affect the behaviour of the studied strains. Some of the flavonoids showed an effect on the production of volatile phenols, although strongly dependent on the bacterial species. Relatively high concentrations (1 g l^?1) of tannins inhibited the synthesis of 4VP by Lact. plantarum. Conclusions: Hydroxycinnamic acids were the main compounds stimulating the production of volatile phenols by LAB. The results suggest that caffeic and ferulic acids induce the synthesis of the cinnamate decarboxylase involved in the metabolism of p‐coumaric acid. On the other hand, tannins exert an inhibitory effect. Significance and Impact of the Study: This study highlights the capacity of LAB to produce volatile phenols and that this activity is markedly influenced by the phenolic composition of the medium.     

Trichogramma parasitoids for control of Lepidopteran borers in Taiwan: species,life‐history traits and Wolbachia infections

Trichogramma, polyphagous endoparasitoids of lepidopteran eggs, are used against a variety of crop pests throughout the world including those of sugar cane and corn in south‐eastern Asia. Their ability to be easily and economically reared on factitious hosts and their wide host range have contributed to their widespread use in pest control. The overall aim of this study was to select strains for eventual release in crop areas for control of lepidopteran borer pests of sugar cane and corn. To this end, we identified common Trichogramma species emerging from corn borer egg masses throughout south‐western Taiwan, compared their life‐history characteristics, assessed their thermal limits and identified the Wolbachia infection status of collected Trichogramma parasitoids. Trichogramma ostriniae was the most commonly collected species on corn, with occasional detection of T. chilonis and an unidentified species designated as T. sp. y. Although the sex ratio varied widely between sites, Wolbachia infection was detected only at a single site in one species (T. ostriniae). Wolbachia‐infected T. ostriniae were tolerant to high temperature stress. Trichogramma chilonis had lowest fecundity of the three species tested, and a Wolbachia‐infected T. ostriniae strain had lower fecundity than an uninfected strain. Given the limited availability of distribution and historical data for Trichogramma species in Taiwan, the current study provides a baseline for future work and also highlights the importance of accurately identifying species when establishing colonies of natural enemies for biocontrol.     

Importance of host oviposition pattern and plant size for the selection of Trichogramma strains to control the diamondback moth

The aim of this work was to select a candidate strain of Trichogrammatidae (Hymenoptera: Chalcidoidea) to control the diamondback moth, Plutella xylostella L. (Lepidoptera: Plutellidae), an important pest of cabbage in Europe. The parasitic efficiency of Trichogramma chilonis Ishii from Japan and Réunion Island, Trichogramma evanescens Westwood from Egypt, Trichogramma ostriniae Pang & Chen from Japan, and Trichogramma semblidis (Aurivillius) from France was studied with sentinel eggs in greenhouse‐grown cauliflower. The percentage of parasitized eggs was measured 1 m from the release point and 3 days after release. Two factors were studied: host‐egg density (three eggs per stem vs. 50 eggs per stem) and plant size (50–100 cm high plants vs. 100–150 cm high plants). Trichogramma evanescens from Egypt achieved the best parasitism. Parasitism efficiency of T. ostriniae from Japan and T. chilonis from Réunion Island was not influenced by egg density. In contrast, parasitism efficiencies of the three other strains were higher at the lower egg density than at the higher egg density. Parasitism efficiency was lower when the plants were bigger, with the exception of T. chilonis from Réunion Island, for which the level of parasitism was not affected by plant size. Thus, T. chilonis from Réunion Island appeared to be the most suitable Trichogramma strain for use in controlling P. xylostella, regardless of the growth stage of the crop. However, T. ostriniae from Japan may also be more suitable for use on cauliflower crops at the early stage of crop development. If potential problems related to the introduction of exotic species are taken into consideration, it is possible to consider the native T. evanescens.     

Enhanced production of the pharmaceutically important polyphenolic compounds in Vitex agnus castus L. shoot cultures by precursor feeding strategy

Agitated Vitex agnus castus L. shoot cultures were established to analyse the content of selected pharmaceutically important flavonoids and phenolic acids. Two variants (selected from nine ones) of MS medium were prepared: A (BAP 1 mg/L; NAA 0.5 mg/L; GA₃ 0.25 mg/L) and B (BAP 2 mg/L; NAA 0.5 mg/L). The biomass was harvested after 1, 2, 3,4, 5 and 6 weeks. Four‐week cultures (variant A) were selected to perform the precursor feeding experiment. The L‐phenylalanine dose of 1.6 g/L appears to be the most advantageous. Compared to the control cultures, the content of the individual compounds increased in a range from 1.4 to 17.3‐fold (e.g. p‐coumaric acid – 17.3 fold; casticin – 4.8‐fold). The biomass from in vitro cultures is richer in neochlorogenic acid (16‐fold), p‐coumaric acid (5.3‐fold), rutin (2.8‐fold), caffeic acid (1.5‐fold) and cinaroside (1.5‐fold) than the leaves of its parent greenhouse‐cultivated plants. Extracts contained 30 mg/100 g DW of casticin, but after the hydrolysis its amount increased up to 200 mg/100 g DW and twice exceeded the content in the greenhouse leaves. The results indicate that V. agnus castus agitated shoot cultures might be considered as a potential biotechnological source of some pharmaceutically important compounds, especially casticin, rutin, neochlorogenic and p‐coumaric acids.     

A Comparative Study on Polyphenolic Composition of Berries from the Tibetan Plateau by UPLC‐Q‐Orbitrap MS System

Five traditional medicinal food from the Tibetan plateau including Nitraria tangutorum Bobrov (NT), Hippophae rhamnoides L. (HR), Lycium ruthenicum Murray (LR), Lycium barbarum L. (LB) and Rubus corchorifolius L.f. (RC) are rich in phenolic compounds. However, the detailed studies about the phenolic compounds remain scarce. Therefore, we established a rapid method for the simultaneous identification and quantification of the phenolic compounds from berries via Ultra Performance Liquid Chromatography‐Quadruple‐Orbitrap MS system (UPLC‐Q‐Orbitrap MS). This method was verified from many aspects including detection limit, quantification limit, precision, repeatability, stability, average recovery rate and recovery range, and then was used to analyze the phenolic compounds in these five species of berries. Finally, a total of 21 phenolic compounds were directly identified by comparing the retention time and exact mass, of which 14 compounds were identified by us for the first time in berries from the Tibetan plateau, including one flavonoid aglycone (myricetin), 11 phenolic acids (gallic acid, protocatechuate, chlorogenic acid, vanillic acid, caffeic acid, syringic acid, p‐coumaric acid, ferulic acid, 2‐hydroxybenzeneacetic acid and ellagic acid), one flavanol (catechin) and one dihydrochalcone flavonoid (phloretin). Quantitative results showed that rutin, myricetin, quercetin and kaempferol were the main flavonoids. Moreover, a variety of phenolic acid compounds were also detected in most of the berries from the Tibetan plateau. Among these compounds, the contents of protocatechuate and chlorogenic acid were high, and high levels of catechin and phloretin were also detected in these plateau berries.     

Orientation behaviour of Helicoverpa armigera egg parasitoid,Trichogramma chilonis and the larval parasitoid,Campoletis chlorideae towards different groundnut genotypes

Behavioural responses of Helicoverpa armigera egg parasitoid, Trichogramma chilonis and the larval parasitoid, Campoletis chlorideae towards the leaves of groundnut (Arachis hypogaea) genotypes (ICGV 86699, ICGV 86031, ICG 2271, and ICG 1697-resistant, and the susceptible check-JL 24) were studied by using a Y-tube olfactometer. Orientation was studied in comparison to clean air, to insect resistant genotypes in relation to JL 24 and towards H. armigera damaged and undamaged leaves. Leaves of ICGV 86699, ICGV 86031 and ICG 2271 were more attractive to T. chilonis adults than to the clean air. They were strongly attracted to the leaves of ICGV 86699, ICGV 86031 and ICG 1697 than of JL 24. Insect damaged leaves of ICGV 86699, ICGV 86031 and ICG 1697 were more attractive than the respective uninfested leaves. C. chlorideae showed greater attraction towards leaves of ICGV 86699, ICG 2271 and ICG 1697 than the clean air, and were more attracted towards leaves of ICGV 86699 and ICGV 86031 than those of JL 24. The damaged leaves of ICGV 86699, ICGV 86031 and ICG 2271 were more attractive to C. chlorideae than the respective uninfested leaves. Thus insect resistant genotypes exhibited greater compatibility with the natural enemies in groundnut.     

The Effectiveness of Trichogramma chilonis,Trichogramma pretiosum and Trichogramma brasiliense (Hymenoptera: Trichogrammatidae) as Parasitoids of Helicoverpa armigera (Lepidoptera: Noctuidae) on Sunflower (Helianthus annuus) and Redgram (Cajanus cajan)

The performance of three species of trichogrammatids on the pest, Helicoverpa armigera was evaluated in the laboratory and screenhouse conditions in Karnataka, India during 1996-97. Laboratory studies indicated that Trichogramma chilonis and Trichogramma pretiosum were more effective parasitoids of H. armigera than Trichogramma brasiliense. In screenhouse conditions, T. chilonis was the most effective parasitoid of H. armigera eggs on sunflower plants in comparison to the other two trichogrammatid species. When releasing 50?000 per ha on sunflower and redgram, T. chilonis parasitised 50.1 and 11.4% H. armigera eggs, respectively. The position of H. armigera eggs on different plant parts of sunflower had no effect on parasitism by T. chilonis. However, parasitism by the same trichogrammatid among different plant parts of redgram varied significantly. It parasitized 43.4 and 18.7% H. armigera eggs on leaves and flowers, respectively, and significantly fewer, 3.9%, on pods (P&lt;0.05). The growth stage of redgram plants also had an effect on parasitism by T. chilonis, parasitism being extremely low on plants with pods.     

Chemical Characterization and Phytotoxic Effects of the Aerial Parts of Ruzigrass (Urochloa ruziziensis)

Studies of the phytotoxic effects between plants can be a crucial tool in the discovery of innovative compounds with herbicide potential. In this sense, we can highlight ruzigrass (Urochloa ruziziensis), which is traditionally used in the crop rotation system in order to reduce weed emergence. The aim of this work was to characterize the secondary metabolites of ruzigrass and to evaluate its phytotoxic effects. In total, eight compounds were isolated: friedelin, oleanolic acid, α‐amyrin, 1‐dehydrodiosgenone, sitosterol and stigmasterol glycosides, tricin and p‐coumaric acid. Phytotoxic effects of the crude methanolic extract and fractions of ruzigrass were assessed using germination rate, initial seedling growth, and biomass of Bidens pilosa, Euphorbia heterophylla and Ipomoea grandifolia. Chemometric analysis discriminated the weed species into three groups, and B. pilosa was the most affected by fractions of ruzigrass. The phytotoxic activities of 1‐dehydrodiosgenone, tricin, and p‐coumaric acid are also reported, and p‐coumaric acid and 1‐dehydrodiosgenone were active against B. pilosa.     

Phenolic Compounds and Allelopathic Potential of Fermented and Unfermented Wheat and Corn Straw Extracts

Total phenolic (TPC) and flavonoid (TFC) content, individual phenolic compounds and antioxidant activities of methanol extracts of wheat and corn straw were determined. Germination bioassay was conducted with Abutilon theophrasti Medik. , Asclepias syriaca L., and Chenopodium album L. seed. Samples were fermented by Lactobacillus plantarum and changes in TPC, TFC, antioxidant, and biological activity were investigated. TPC and TFC were significant in both samples and after fermentation their recovery was improved. All samples contain mainly quercetin, cinnamic acid, p‐coumaric acid, and ferulic acid. Fermentation changed the content of phenolic and flavonoid compounds, differently in each case. All tested extracts showed high DPPH activity with IC₅₀ being significantly lower for fermented samples. FRAP activity was also high. Crude straw extracts were overall more effective than fermented ones concerning inhibition of germination and seedlings growth, mainly without statistically significant differences between wheat and corn. Compared with mesotrione, extracts were more effective in germination and seedling growth inhibition of C. album and in seedling growth inhibition of A. theophrasti.     

Dietary plant phenolic improves survival of bacterial infection in Manduca sexta caterpillars

Plant phenolics are generally thought to play significant roles in plant defense against herbivores and pathogens. Many plant taxa, including Solanaceae, are rich in phenolic compounds and some insect herbivores have been shown to acquire phenolics from their hosts to use them as protection against their natural enemies. Here, we demonstrate that larvae of an insect specialist on Solanaceae, the tobacco hornworm, Manduca sexta L. (Lepidoptera: Sphingidae), acquire the plant phenolic chlorogenic acid (CA), and other caffeic acid derivatives as they feed on one of their hosts, Nicotiana attenuata L. (Solanaceae), and on artificial diet supplemented with CA. We test the hypothesis that larvae fed on CA‐supplemented diet would have better resistance against bacterial infection than larvae fed on a standard CA‐free diet by injecting bacteria into the hemocoel of fourth instars. Larvae fed CA‐supplemented diet show significantly higher survival of infection with Enterococcus faecalis (Andrewes & Horder) Schleifer & Kilpper‐Bälz, but not of infection with the more virulent Pseudomonas aeruginosa (Schroeter) Migula. Larvae fed on CA‐supplemented diet possess a constitutively higher number of circulating hemocytes than larvae fed on the standard diet, but we found no other evidence of increased immune system activity, nor were larvae fed on CA‐supplemented diet better able to suppress bacterial proliferation early in the infection. Thus, our data suggest an additional defensive function of CA to the direct toxic inhibition of pathogen proliferation in the gut.     

Production of Substituted Styrene Bioproducts from Lignin and Lignocellulose Using Engineered Pseudomonas putida KT2440

Ferulic acid is a renewable chemical found in lignocellulose from grasses such as wheat straw and sugarcane. Pseudomonas putida is able to liberate and metabolize ferulic acid from plant biomass. Deletion of the hydroxycinnamoyl‐CoA hydratase‐lyase gene (ech) produced a strain of P. putida unable to utilize ferulic and p‐coumaric acid, which is able to accumulate ferulic acid and p‐coumaric acid from wheat straw or sugar cane bagasse. Further engineering of this strain saw the replacement of ech with the phenolic acid decarboxylase padC, which converts p‐coumaric and ferulic acid into 4‐vinylphenol and the flavor agent 4‐vinylguaiacol, respectively. The engineered strain containing padC is able to generate 4‐vinylguaiacol and 4‐vinylphenol from media containing lignocellulose or Green Value Protobind lignin as feedstock, and does not require the addition of an exogenous inducer molecule. Biopolymerization of 4‐vinylguaiacol and 4‐vinylcatechol styrene products is also carried out, using Trametes versicolor laccase, to generate “biopolystyrene” materials on small scale.     

Increased accumulation of phenolic metabolites in groundnut (Arachis hypogaea L.) genotypes contribute to defense against Sclerotium rolfsii infection

Abstract

Fungal infections cause several metabolic changes to the plants, which can affect its physiology and survival in various ways. In the present study, we have analysed various phenolic compounds and activity of oxidative enzymes in healthy and Sclerotium rolfsii-infected groundnut genotypes. Increased phenolics content and higher activity of oxidative enzymes was observed in the tolerant genotype (CS 19, GG 16) followed by susceptible genotype (GG 20, TG 37A). Among the phenolic compounds tested, chlorogenic acid content has increased greatly in leaf, stem and root of infected tolerant genotypes compared to the respective controls. In vitro growth of S. rolfsii showed significant inhibition at concentrations 500 and 1000 µg/mL of phenolic compounds in the radial growth inhibition assay. These results have strongly suggested that, higher accumulation of chlorogenic acid could be an important factor in imparting resistance and protecting groundnut against S. rolfsii infection in tolerant genotypes.     

Selected Allelochemicals

Extensive research work has been done on allelochemicals that are primarily plant secondary metabolites; in this review, some pathways of biosynthesis that are produced by higher plants are discussed as well as plant defense and the potential of the control of pests, diseases, and weeds. Benzoxazinoids, glucosinolates, and some sesquiterpenoids and phenolic compounds are discussed in more detail. Five genes, Bx1 through Bx5, have been analyzed and shown to be required for a typical benzoxazinoid, DIMBOA biosynthesis in maize, and their functions were demonstrated in vitro. Among those alleochemicals mentioned here, some isothiocyanates hirsutin and ω methylsulfonylalkyl (n=8, 9, and 10) isothiocyanates, sesquiterpenoids rugosal A and lettucenin A, and phenolic compounds emodin, physcion, p-hydroxybenzaldehyde, p-hydroxybenzoic acid, and oligostilbenes are emphasized from the viewpoint of plant defense.     

Preparation and biological assessment of hydroxycinnamic acid amides of polyamines

Many plants contain hydroxycinnamic acid conjugates of polyamines that are remarkably similar in general structure to the acylated polyamines found in spider and wasp toxins. In an effort to determine whether these compounds might play a role in the chemical defense of plants against arthropod pests we synthesized a variety of analogues of the coumaric (4-hydroxycinnamic) acid conjugates of di-, tri-, and tetraamines using common protection and acylation strategies. N(1)- and N(8)-coumaroyl spermidine were tested in feeding trials with insect larvae including the European corn borer (Ostrinia nubilalis), the tobacco budworm (Heliothis verescens) and the oblique banded leaf roller (Choristoneura rosaceana). Antifeedant assays with the rice weevil Sitophilus oryzae were also performed. Neither the naturally occurring coumaric acid conjugates of polyamines nor their analogues showed notable toxicity towards insects, despite precautions to maintain these easily oxidized materials in the wet diet. However, more direct bioassays of these compounds on glutamate dependent neuroreceptors including the deep abdominal extensor muscles of crayfish, or mammalian NMDA, delta2, and AMPA receptors, clearly showed that these compounds were inhibitory. N(1)-Coumaoryl spermine, a dodecyl and a cyclohexyl analogue were especially active at NMDA NR1/NR2B receptors. The latter had an IC(50) of 300 microM in the crayfish. N(1)-Coumaroyl spermine had an IC(50) in the crayfish preparation of 70-300 microM and against the mammalian NR1/NR2B receptor of 38 nM. Structure-activity variations show similar trends of length and hydrophobicity as has been seen previously with analogues of spider toxins. We conclude from this work that while the coumaric acid polyamine conjugates are active when directly applied to neuroreceptors, they show no overt toxicity when ingested by insect larvae.