Evaluation of phytotoxic potential and identification of phytotoxic substances in Cassia alata Linn. leaves

Cassia alata (Caesalpiniaceae) is a large perennial shrub native to tropical America. It is an important medicinal and ornamental plant and has been reported to possess several pharmacological properties. However, phytotoxic substances from C. alata have not yet been documented in the literature. Therefore, this study seeks to evaluate the phytotoxic potential of C. alata leaves and to identify inhibitory substances for the purpose of eco-friendly weed management. The effect of aqueous methanol extracts of C. alata on the seedling growth of alfalfa, cress, lettuce, rapeseed, barnyard grass, foxtail fescue, Italian ryegrass, and timothy was examined. The level of inhibition of the extracts corresponded to concentration. Several chromatographic steps were performed to separate the extracts, and through spectroscopic analysis, two active substances were isolated and characterised as rutin and syringone. These two active substances significantly inhibited the seedling growth of cress and foxtail fescue. The range of I₅₀ values (required concentration for 50% growth inhibition) of rutin and syringone for the seedling growth of cress and foxtail fescue were 129.5–417.8 and 160.1–466.5?µM, respectively. These results indicate that the two identified active phytotoxic substances from C. alata may be responsible for its growth inhibitory properties.     

Summary of phytotoxic levels of soil arsenic

In the absence of site-specific data, generic guidelines are important to indicate whether soils contaminated with As require attention or remediation. It is important that the data used to set generic guidelines come from as broad a survey as possible. The objective of this paper is to summarize the data on the phytotoxicity of As from the literature, and to analyze the associated variance. The very narrow margin between background and toxic concentrations of As in soils is clearly shown. The source of As is important; the inorganic sources are less toxic than the organic sources. When only the inorganic sources are considered, soil type is the only other significant variable. Monocotyledonous and dicotyledonous plants did not differ significantly in response to soil As. Inorganic As is 5-fold more toxic in sands and loams (the geometric mean, GM, of the reported toxicity thresholds is 40 mg kg^?1) than in clay soils (where the GM is 200 mg kg^?1). Deviation of a single geometric standard deviation is 3.6-fold above and below these GM values. The results show that it is appropriate to set generic regulatory criteria by soil type, but that site- or soil-specific data is likely needed past a screening stage.     

Determination of phytotoxic soil aluminium by electroultrafiltration

The experiments address the questions of whether phytotoxic Al can be determined by electroultrafiltration (EUF). Spring barley (Hordeum vulgare) was grown in pot experiments on 28 soils differing widely in their characteristics. Al toxicity was measured in terms of root parameters and top growth. On soils rich in EUF extractable Al typical Al toxicity symptoms were found in roots and tops. EUF extractable Al obtained at the cathode (EUF-Al, cathode) was correlated with root fresh weight (R² = 0.554), root length (R² = 0.653), root diameter (R² = 0.729) and fresh weight of tops (R² = 0.681). The Al obtained at the anode was not correlated with any of these plant parameters. It is supposed that this anionic Al consists of non toxic organic Al complexes. Correlations between plant parameters and KCl-exchangeable Al were less close than those for EUF-Al (cathode). Correlations between soil pH and plant parameters were in between the correlations for exchangeable Al and EUF-Al (cathode).     

Tagetolone and tagetenolone: two phytotoxic polyketides from Alternaria tagetica

Two new phytotoxic polyketides, tagetolone (1) and tagetenolone (2), in addition to tyrosol and p-hydroxybenzoic acid, have been isolated from the organic crude extract of culture filtrates from the fungal pathogen Alternaria tagetica. Complete characterization of all structures was carried out following a careful analysis of their spectroscopic data (IR, MS, (1)H and (13)C NMR, and 2D NMR experiments).     

Synthesis and herbicidal activity of N-oxide derivatives

As part of an ongoing program on the chemistry and biological activity of N-oxide-containing molecules, a number of novel 1,2, 5-oxadiazole N-oxide, benzo[1,2-c]1,2,5-oxadiazole N-oxide, and quinoxaline N,N'-dioxide derivatives were synthesized and evaluated for their herbicidal activity. Many of these compounds exhibited moderate to good herbicidal pre-emergence activity against Triticum aestivum. Dose-response studies were done on the more representative compounds (12, 20, and 26). The most active compound, butylcarbamoylbenzo[1,2-c]1,2,5-oxadiazole N-oxide, 26, displayed herbicidal activity at concentrations as low as 24 g/ha.     

Nutrient and phytotoxic contributions of residue to soil in no-till continuous-corn ecosystems

Summary An understanding of no-till ecosystems is essential for increased acceptance of conservation tillage practices. The primary objective of the present research was to assess the nutrient contributions of leachates from decomposing corn residue to soil in continuous-corn no-till ecosystems. A secondary objective was to estimate the phytotoxic effects of these leachates on corn seedling growth. The effects of moisture, temperature, and resident and non-resident microflora on leachates recovered from decomposing surface-applied corn residue were also studied. Leachates were analyzed for organic C, total N, PO ₄ ^3– -P, acid and alkaline phosphatase activity, urease activity, and phytotoxic effects. Within the first 90 days of a 215-day field study 73%, 83%, and 60% of C, N, and P, respectively, were leached. In terms of nutrient concentration, this suggests two distinct phases of release of nutrients onto the soil: A high initial flux of nutrients that is followed by a low-concentration release. No phytotoxic effect of field leachates was observed. Acid and alkaline phosphatase activity was highest on days 39 and 47 whereas urease activity peaked on day 149. In laboratory studies, alterations in temperature or moisture had little effect on the leachate nutrient concentration, or phytotoxic or enzyme activity. Increasing amounts of organic C and N were extracted over time. No phytotoxic effects were expressed in the laboratory. Overall, it appears that the maximum leaching of nutrients occurs early in the decomposition process and that in no-till systems no phytotoxicity can be associated with decomposition of surface residues.Paper No. 11871 of the Purdue University Agricultural Experiment Station Series     

Synthesis and fungicidal activity of novel 2-oxocycloalkylsulfonylureas

A series of 2-oxocycloalkylsulfonylureas (2) have been synthesized in a six-step, three-pot reaction sequence from readily available cyclododecanone, cycloheptanone, and cyclohexanone. Their structures were confirmed by IR, 1H NMR, and elemental analysis. The bioassay indicated that some of them possess certain fungicidal activity against Gibberella zeae Petch. In general, compounds containing a 12-membered ring (2A) are more active than those containing a 6- or 7-membered ring (2B, 2C). In the series 2A, the compounds in which R is a disubstituted phenyl or pyrimidyl showed better activity than those in which R is a monosubstituted phenyl or pyrimidyl, and aryl-substituted compounds have somewhat higher activity than those substituted by pyrimidyl. The further bioassay showed that the representative of 2A, 2A15, has good fungicidal activities against not only G. zeae Petch but also Botrytis cinerea Pers, Colletotrichum orbiculare Arx, Pythium aphanidermatum Fitzp, Fusarium oxysporum Schl. f. sp. Vasinfectum, etc.     

Synthesis and antifungal activity of novel sclerotiorin analogues

Sclerotiorin 1, first isolated from Penicillium sclerotiorum, has weak antifungal activity and belongs to the azaphilone-type family of natural products. Several series of sclerotiorin analogues were designed and synthesized with the aim of discovering novel fungicides with improved activity. The syntheses involved two key steps, cycloisomerization and then oxidation, and used a simple and efficient Sonogashira cross-coupling reaction to construct the required functionalized precursor. With sclerotiorin as a control, the activities of the newly synthesized analogues were evaluated against seven fungal pathogens, and several promising candidates (compounds 3a?, 3d?, 3e?, 3f? and 3k?) with greater activity and simpler structures than sclerotiorin were discovered. In addition, preliminary structure-activity relationships were studied, which revealed that not only the chlorine or bromine substituent at the 5-position of the nucleus but also the phenyl group at the 3-position and the substituent pattern on it contributed crucially to the observed antifungal activity. Analogues with a methyl substituent at the 1-position have reduced levels of activity, while those with a free hydroxyl group in place of acetoxy at the quaternary center of the bicyclic ring system retain activity.     

Characterization of phytotoxic aluminum in soil solutions from phosphogypsum amended soils

Phosphogypsum (PG), an industrial by-product from phosphoric acid plants, is being used as an ameliorant for acid soil infertility. Phosphogypsum is primarily CaSO₄ and contains F among several impurities. An increase in SO₄ ^2– and F^– ligands in soil solutions following amendment with PG is important for the alleviation of Al toxicity. In soil solutions containing abundant SO₄ ^2– and F^–, a measure of Al that is not complexed with either of the ligands represents phytotoxic Al. Alleviation of Al toxicity by SO₄ ^2– in some instances is due to SO₄ ^2–-induced precipitation and/or sorption of Al. Some studies have demonstrated a decrease in Al toxicity by SO₄ ^2– even though precipitation of Al was not evident.In such cases, formation of the Al-SO₄ ⁺ ion-pair (predicted by speciation models) has been attributed as the reason for alleviation of Al toxicity. Recent evidence has indicated that the proportion of Al complexed with SO₄ ^2– was much greater than that predicted by using speciation models, which suggests that alleviation is not fully attributable to the formation of AlSO₄ ⁺ species. The existing colorimetric Al assay techniques have failed to discriminate Al complexed with SO₄ ^2– and have therefore, proved to be unsuitable for determination of phytotoxic Al in solutions containing SO₄ ^2–. Fractionation of Al complexed with SO₄ ^2– by size exclusion chromatography (SEC) has permitted a more precise characterization of Al complexed with SO₄ ^2– which has been demonstrated as less phytotoxic than the uncomplexed Al. Therefore, size exclusion chromatography is a promising technique for characterization of phytotoxic Al in solutions in the presence of SO₄ ^2–. In solutions containing F^–, alleviation of Al toxicity is due to formation of Al-F complexes which are less phytotoxic. The 8-hydroxyquinoline method with a 15 second reaction time excludes Al-F complexes and, therefore is a measure of phytotoxic Al in solutions containing F^–.     

Synthesis and antiviral activity of novel chiral cyanoacrylate derivatives

2-Cyanoacrylate is an important kind of herbicide targeted in photosystem II. Starting from cyano ethyl acetate, the chiral title compounds were synthesized under microwave irradiation, which has the advantages of shorter reaction time, higher yield, and simpler procedure. A half-leaf method was used to determine the inhibition and curative efficacies of the eight chiral products against tobacco mosaic virus in vivo. It was found that chiral compound IIc-R possesses moderate inhibition and curative effect in vivo with rates of 89.1 and 43.1%, respectively. In the MTT test, these new chiral compounds were found to possess weak antiproliferation activities to PC3 and A431 cells.     

Promotion of phytotoxic bacteria in rhizospheres of leatherleaf fern by benlate DF

Foliar damage symptoms to leatherleaf fern (Rumohra adiantiformis [Forst] Ching) in Florida during widespread use of the fungicide Benlate DF could not be attributed to nutrition, cultural practices, environmental conditions, or new pathogens developing on the crop. The objective of this study was to assess the involvement of rhizosphere bacteria in the damage symptoms using bioassays to detect phytotoxic activity. Rhizosphere bacteria were cultured from rhizospheres of leatherleaf ferns sampled from ferneries where Benlate DF was routinely applied and from check ferneries not receiving the fungicide. Using a lettuce seedling bioassay, the proportion of rhizosphere bacteria that was plant growth‐inhibitory ranged from 7.5% and 11% for isolates from two check ferneries to 70% for those from a fernery previously treated with Benlate DF. Rhizosphere bacteria originating from Benlate DF‐treated leatherleaf ferns caused most severe damage on seedlings with some isolates reducing root growth 70% compared to control seedlings. Other symptoms induced by these bacteria, which were mainly fluorescent and nonfluorescent pseudomonads, included necroses and inhibition of root hair development. Results suggested that Benlate DF affected the composition of bacteria in leatherleaf fern rhizospheres by promoting a bacterial component with phytotoxic properties toward plant growth.     

Synthesis and herbicidal activity of 2-cyano-3-substituted-pyridinemethylaminoacrylates

Two series of 2-cyano-3-substituted-pyridinemethylaminoacrylates, namely 12 new (Z)-2-cyano-3-methylthio-3-substituted-pyridinemethaneaminoacrylates and 10 new (Z)-2-cyano-3-alkyl-3-substituted-pyridinemethaneaminoacrylates, were synthesized as herbicidal inhibitors of photosystem II (PSII) electron transport. All of these compounds were confirmed by (1)H NMR, elemental, IR, and mass spectrum analyses. Their herbicidal activities were evaluated. Some compounds exhibited excellent herbicidal activities, even at a dose of 75 g/ha. A suitable substituent at the 2-position of the pyridine ring and the well-fit group at the 3-position of acrylate were essential for high herbicidal activity. 2-Cyanoacrylates containing a substituted pyridine ring provide higher herbicidal activities than parent compounds containing phenyl. These PSII inhibitor herbicides are safe to corn, which is a major crop in China.     

Synthesis, fungicidal activity, and QSAR of pyridazinonethiadiazoles

A series of novel 5-[1-aryl-1,4-dihydro-6-methylpyridazin-4-one-3-yl]-2-arylamino-1,3,4-thiadiazoles, related to the fungicidal activity, were synthesized and tested in vivo against wheat leaf rust, Puccinia recondita. The preliminary bioassay indicated that they exhibited fungicidal activity and the activity was influenced by the nature of the substituents. A quantitative structure-activity relationship study showed that the hydrophobicity (Sigma(pi)) is a major positive parameter in affecting the activity; the electronic parameters (Sigmasigma, SigmaF) are the major negative parameters in affecting the activity. Especially, introducing an ortho substituent with an inductively electron-donating property is favorable to the activity.     

Isolation of phytotoxic compounds from tree-of-heaven (Ailanthus altissima swingle)

The aqueous root extract of Ailanthus altissima showed allelopathic activity against radish (Raphanus sativus L. cv. "Saxa"), garden cress (Lepidium sativum L.), and purslane (Portulaca oleracea L.) seeds. A bioassay-oriented purification of active extracts, chromatographic fractions, and compounds demonstrated dose-dependent activity on germination and radicle growth of test seeds; radish seed was the most sensitive to allelochemicals. Active compounds have been isolated: ailanthone, ailanthinone, chaparrine, and ailanthinol B (quassinoid derivatives); the alkaloid 1-methoxycanthin-6-one is not active. The compound with greatest inhibitory activity is ailanthone. The data obtained suggest a possible use of tree-of-heaven root extracts or of its active constituents as natural herbicides.     

Synthesis and insecticidal activity of some novel fraxinellone-based esters

In continuation of a program aimed at the discovery and development of natural products-based insecticidal agents, two series of novel fraxinellone-based esters were synthesized by modification at the C-4 or C-10 position of fraxinellone and evaluated for their insecticidal activity against the pre-third-instar larvae of Mythimna separata in vivo. An efficient method for the stereoselective synthesis of 4α-hydroxyfraxinellone from fraxinellonone was developed, and the steric configuration of 6h was unambiguously confirmed by X-ray crystallography. Among 37 compounds, some derivatives displayed potent insecticidal activity; especially compounds 6h, 6q, 6t, and 7q showed more promising insecticidal activity than toosendanin, a commercial botanical insecticide derived from Melia azedarach . This suggested that introduction of the fluorine atom on the phenyl ring could lead to a more potent compound than one possessing chlorine or bromine. Meanwhile, introduction of the heterocyclic fragments at the C-4 or C-10 position of fraxinellone was essential for their insecticidal activity. This will pave the way for further design, structural modification, and development of fraxinellone as an insecticidal agent.     

Dihydropiperazine neonicotinoid compounds. Synthesis and insecticidal activity

Syntheses of various isomeric dihydropiperazines can be approached successfully by taking advantage of the regioselective monothionation of their respective diones. Preparation of the precursor unsymmetrical N-substituted piperazinediones from readily available diamines is key to this selectivity. The dihydropiperazine ring system, as exemplified in 1-[(6-chloropyridin-3-yl)methyl]-4-methyl-3-oxopiperazin-2-ylidenecyanamide (4) and 1-[(2-chloro-1,3-thiazol-5-yl)methyl]-4-methyl-3-oxopiperazin-2-ylidenecyanamide (25), has been shown to be a suitable bioisosteric replacement for the imidazolidine ring system contained in neonicotinoid compounds. However, placement of the cyanoimino electron-withdrawing group further removed from the pyridine ring, as in 4-[(6-chloropyridin-3-yl)methyl]-3-oxopiperazin-2-ylidenecyanamide (3a), or relocation of the carbonyl group, as in 1-[(6-chloropyridin-3-yl)methyl]-4-methyl-5-oxopiperazin-2-ylidenecyanamide (5), results in significantly decreased bioisosterism. The dihydropiperazine ring system of 4 and 25 also lends a degree of rigidity to the molecule that is not offered by the inactive acyclic counterpart 2-[(6-chloropyridin-3-yl)-methyl-(methyl)amino]-2-(cyanoimino)-N,N-dimethylacetamide (6). A pharmacophore model is proposed that qualitatively explains the results on the basis of good overlap of the key pharmacophore elements of 4 and imidacloprid (1); the less active regioisomers of 4 (3a, 5, and 6) feature a smaller degree of overlap.     

Herbicidal potential of stagonolide, a new phytotoxic nonenolide from Stagonospora cirsii

Stagonospora cirsii is a pathogen of Cirsium arvense, causing necrotic lesions on leaves of this noxious weed. The fungus produced toxic metabolites when grown in liquid culture. A new phytotoxin, named stagonolide, was isolated and characterized as (8R,9R)-8-hydroxy-7-oxo-9-propyl-5-nonen-9-olide by spectroscopic methods. Stagonolide was shown to be a nonhost-specific but selective phytotoxin. Leaves of C. arvense were most sensitive and leaves of tomato and pepper (both Solanaceae) were less sensitive to stagonolide, which was assayed at 5 x 10(-3) M, than other plants. Stagonolide assayed at 5 x 10(-6) M was demonstrated to be a strong inhibitor of root growth in seedlings of C. arvense and some other Asteraceae species. Seedlings growth in wheat and radish was much less affected by the toxin, and seedlings of cucumber were insensitive to it.     

Synthesis and biological activity of enantiomeric pairs of phosphosulfonate herbicides

The phosphosulfonates are a new class of soil-active herbicides which control a variety of annual grass and broadleaf weeds. Chirality at the phosphorus atom afforded the opportunity to explore stereospecific requirements for herbicidal activity. Chiral (hydroxymethyl)phosphinate intermediates were enzymatically resolved (Pseudomonas fluorescens lipase) from the racemic mixtures and then used to prepare two pairs of enantiomeric phosphosulfonates. Biological testing of the enantiomeric phosphosulfonate herbicides demonstrated that, in each case, the herbicidal activity was attributed to the (+) enantiomer and that the (+) enantiomer is more active than the racemate.