1-Cyano-2-Hydroxy-3-Butene, A Phytotoxin From Crambe (Crambe abyssinica) Seedmeal

Crambe (Crambe abyssinica) seedmeal was found to suppress seedling emergence and biomass accumulation when added to a sandy loam soil containing wheat (Triticum aestivum Cardinal) and hemp sesbania (Sesbania exahata) seeds. Hexane, CH₂Cl₂, MeOH, and water extracts of the seedmeal were prepared and bioassayed against wheat and velvetleaf (Abutilon theophrasti) radicle elongation. The CH₂Cl₂ extract was the most inhibitory, while the other extracts inhibited the bioassay species only slightly (MeOH) or not at all (hexane, water). Fractionation of the CH₂Cl₂ extract identified the major phytotoxin as l-cyano-2-hydroxy-3-butene (CHB), comprising 96.1% of the active CH₂Cl₂ fraction. Radicle elongation of wheat and velvetleaf were inhibited by CHB with I₅₀ values of 2.1 × 10^–4 M for wheat and 2.7 × l0^–3 M for velvetleaf.     

Allelochemicals Isolated from Tissues of the Invasive Weed Garlic Mustard (Alliaria petiolata)

Garlic mustard (Alliaria petiolata) is a naturalized Eurasian species that has invaded woodlands and degraded habitats in the eastern United States and Canada. Several phytotoxic hydrolysis products of glucosinolates, principally allyl isothiocyanate (AITC) and benzyl isothiocyanate (BzITC), were isolated from dichloromethane extracts of garlic mustard tissues. AITC and BzITC were much more phytotoxic to wheat (Triticum aestivum) than their respective parent glucosinolates sinigrin and glucotropaeolin. However, garden cress (Lepidium sativum) growth was inhibited to a greater degree by glucotropaeolin than BzITC, possibly due to conversion to BzITC by endogenous myrosinase. Sinigrin and glucotropaeolin were not detected in leaf/stem tissues harvested at the initiation of flowering, but were present in leaves and stems harvested in the autumn. Sinigrin levels in roots were similar for both sampling dates, but autumn-harvested roots contained glucotropaeolin at levels over three times higher than spring-harvested roots. The dominance of garlic mustard in forest ecosystems may be attributable in part to release of these phytotoxins, especially from root tissues.     

Toxicity of allyl isothiocyanate-amended soil toLimonius californicus (Mann.) (Coleoptera: Elateridae) wireworms

Acute toxicity of soil amended with allyl isothiocyanate (AITC) to three size classes ofLimonius californicus (Mann.) wireworms was determined in the laboratory. Wireworms were exposed to AITC at initial concentrations of 120–300 nmol/g soil for one day. During this time, extractable AITC concentrations decreased by 66 to 93 %. Probit analysis estimated LC₅₀ values of 238 and 226 nmol/g soil at one day posttreatment for medium and large wireworms, respectively. For small wireworms, LC₅₀ values decreased from 211 to 157 nmol/g soil during 1–137 days posttreatment. Sublethal concentrations of AITC significantly reduced feeding activity of treated wireworms at three posttreatment times and over the entire 137 days. Wireworm weight was not significantly affected by AITC. The potential exists to use glucosinolate-containing plant tissue as an isothiocyanate (ITC) source to reduce crop damage caused byL. californicus wireworms.     

Phytotoxic and Antifungal Compounds from Two <Emphasis Type="Italic">Apiaceae</Emphasis> Species, <Emphasis Type="Italic">Lomatium californicum</Emphasis> and <Emphasis Type="Italic">Ligusticum hultenii</Emphasis>, Rich Sources of Z-ligustilide and Apiol,Respectively

The seeds of two Apiaceae species, Ligusticum hultenii and Lomatium californicum, were investigated. Preliminary bioassays indicated that methylene chloride extracts of seeds of both species contained selective phytotoxic activity against monocots and antifungal activity against Colletotrichum fragariae. Active constituents were isolated by bioassay-guided fractionation, and the structures were elucidated by NMR and GC-MS as apiol and Z-ligustilide, isolated from L. hultenii and L. californicum, respectively. Apiol and Z-ligustilide had I₅₀ values of about 80 and 600 μM, respectively, for inhibition of the growth of Lemna paucicostata. The methylene chloride (CH₂Cl₂) extracts of the seeds and the isolated and purified compounds were tested against the 2-methylisoborneol-producing cyanobacterium (blue-green alga) Oscillatoria perornata, and the green alga Selenastrum capricornutum. The CH₂Cl₂ extracts of both Apiaceae species and apiol were weakly toxic to both species of phytoplankton, while Z-ligustilide was toxic to both with a lowest complete inhibitory concentration (LCIC) of 53 μM. Seeds of L. californicum and L. hultenii were found to be rich sources of Z-ligustilide (97 mg/g of dry seed) and apiol (40 mg/g of dry seed), respectively.     

Induction of Oxidative Stress by Sunflower Phytotoxins in Germinating Mustard Seeds

The aim of this study was to investigate the phytotoxic effect of sunflower on physiological and biochemical processes during germination of mustard seeds (Sinapis alba L. cv. Nakielska). To exclude the involvement of osmotic stress in seed reaction to phytotoxic compounds, we compared the effect of 10% (w/v) water extract from sunflower (Helianthus annuus L. cv. Ogrodowy) leaves and 28.4% (w/v) polyethylene glycol (PEG) 8000 solution characterized by an equal Ψ = −1 MPa. We evaluated (1) the amount of hydrogen peroxide (H₂O₂); (2) activities of antioxidant enzymes: superoxide dismutase, catalase, and glutathione reductase; (3) membrane permeability; and (4) level of malondialdehyde (MDA). Both, sunflower compounds and PEG solutions inhibited mustard seed germination, but only phytotoxins caused an increase in the cell membrane permeability, MDA level, H₂O₂ concentration, and alterations in activities of antioxidant enzymes. Our results demonstrate that despite the activation of the antioxidant system by sunflower phytotoxins, reactive oxygen species accumulation caused cellular damage, which resulted in the decrease of germinability and gradual loss of seed vigor. It seems that the negative effect of sunflower on germination of mustard seeds is mostly because of its toxicity and not to its contribution to osmotic potential.     

Variation in Allyl Isothiocyanate Production Within Brassica Species and Correlation with Fungicidal Activity

Brassica nigra (black mustard) and B. juncea (Indian mustard) genotypes were tested for pathogen suppression and release of allyl isothiocyanate (AITC), a fungitoxic volatile produced in mustard tissue after enzymatic hydrolysis of allyl glucosinolate (sinigrin). In bioassays, 28 genotypes of B. nigra and 35 genotypes of B. juncea were screened for inhibition of the potato pathogens Helminthosporium solani and Verticillium dahliae by volatiles released from macerated leaf tissue. Release of AITC from plant tissue was quantified by gas chromatography; isothiocyanate profiles were determined by headspace analysis. All mustard genotypes produced compounds that suppressed radial growth of both fungi. Growth suppression and AITC release differed significantly (P < 0.001) among genotypes of B. nigra and B. juncea. Mustard treatments releasing >1.2 mg AITC/g plant tissue were fungicidal to both pathogens. Headspace analysis confirmed that allyl glucosinolate was the major glucosinolate in all genotypes of B. nigra tested; most genotypes also produced 2-phenylethyl-isothiocyanate (ITC). Brassica juncea genotypes produced variable amounts of AITC and other volatiles with antimicrobial activity, including 2-phenylethyl-ITC, benzyl-ITC, and 3-butenyl-ITC. Evaluating mustards from geographically diverse locations allowed selection of mustard genotypes that may be useful in breeding programs designed to develop disease-suppressing green manure cultivars.     

Allelochemical regulation of reproduction and seed germination of two BrazilianBaccharis species by phytotoxic trichothecenes

The potent phytotoxic trichothecene roridins and baccharinoids occur naturally in the Brazilian plants,Baccharis coridifolia andB. megapotamica. Biosynthesis of roridins inB. coridifolia appears to be linked to pollination, and the phytotoxins then accumulate in the seed. The roles of the phytotoxins in pollination, seed maturation, and germination of theBaccharis species were investigated. The high production of roridins occurred only in seeds resulting from intraspecific pollination, and the concentration of the toxins in the seeds generally increased with seed maturity. Removal of seed coats from trichothecene-producing BrazilianBaccharis species (B. coridifolia andB. megapotamica) and non-trichothecene-producing AmericanBaccharis species (B. halimifolia andB. glutinosa) resulted in improved seed germination ofB. halimifolia andB. glutinosa but complete inhibition of seed germination ofB. coridifolia andB. megapotamica. Addition of seed coat extracts of the BrazilianBaccharis species of dilute solutions (10^–6g/ml) of roridins or baccharinoids to the decoated seeds ofB. coridifolia andB. megapotamica resulted in germination, while seeds ofB. halimifolia andB. glutinosa were killed by the phytotoxins. Roridins interacted with gibberellic acid, a germination promoter, but not with abscisic acid, a germination inhibitor. The results from this study suggest that macrocyclic trichothecenes have a regulatory role(s) on reproduction and germination of BrazilianBaccharis species in their natural habitat.     

Isolation and identification of (3-methoxyphenyl)acetonitrile as a phytotoxin from meadowfoam (Limnanthes alba) seedmeal

Ethyl ether, ethanol, and water extracts of meadowfoam (Limnanthes alba Hartweg ex. Benth.) seedmeal were prepared and bioassayed against velvetleaf (Abutilon theophrasti Medicus) and wheat (Triticum aestivum L. Cardinal). Both the ethyl ether and ethanol fractions, but not the water extract, inhibited velvetleaf and wheat radicle elongation. Fractionation of the extracts indicated that (3-methoxyphenyl)acetonitrile (3-MPAN) was the active compound from both extracts, comprising >97% of the active ethanol fraction. 3-Methoxybenzyl isothiocyanate, which had been previously shown to be the major breakdown product of glucolimnanthin, the majorL. alba glucosinolate, was not detected in either extract. Radicle elongation of velvetleaf and wheat were inhibited by 3-MPAN with I₅₀ (the concentration required to inhibit growth by 50%) values of approximately 4 × 10^–4 M (velvetleaf) and 7×10^–4 M (wheat).Mention of firms or products does not imply endorsement by the U.S. Department of Agriculture over other firms or products not mentioned.     

CH3 and Cl2 coadsorbed on Si/Cu(100)

X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) studies were used to investigate the reactions of coadsorbed CH₃ and Cl₂ on Si/Cu(100). TPD results showed that the individual exposure of Si/Cu(100) to CH₃ and Cl₂ resulted primarily in the desorption of (CH₃)₃SiH and SiCl₄, respectively. Coadsorption of CH₃ and Cl₂ at specific surface concentrations on Si/Cu(100) resulted in the desorption of (CH₃)_4-xSiCl_x (x ranges from 1 to 3) species. The relative surface concentration of CH₃ and Cl (resulting from Cl₂ dissociation), however, controlled the stoichiometry of the methylchlorosilane product. XPS results suggested that more Si was removed from the Si/Cu(100) surface as gaseous product when CH₃ and Cl₂ were coadsorbed on the surface than when CH₃ and Cl₂ were adsorbed alone.     

Metallkomplexe mit biologisch wichtigen Liganden. CXXIII. Darstellung von Isophthaloyl‐ und Terephthaloyl‐di‐[(β,γ,δ)‐amino‐α‐aminocarboxylat]‐verbrückten zweikernigen Ruthenium‐, Rhodium‐ und Iridium‐Halbsandwich‐Komplexen

The reaction of the Cu(II) bis N,O‐chelate‐complexes of L‐2,4‐diaminobutyric acid, L‐ornithine and L‐lysine {Cu[H₂N–CH(COO)(CH₂)_nNH₃]₂}²⁺(Cl^–)₂ (n = 2–4) with terephthaloyl dichloride or isophthaloyl dichloride gives the polymeric complexes {‐OC–C₆H₄–CO–NH–(CH₂)_n–CH(nh₂)(COO)Cu(OOC)(NH₂)CH–CH₂)_n–NH‐}_x 1 – 5 . From these the metal can be removed by precipitation of Cu(II) with H₂S. The liberated ω,ω′‐N,N′‐diterephthaloyl (or iso‐phthaloyl)‐diaminoacids 6 – 10 react with [Ru(cymene)Cl₂]₂, [Ru(C₆Me₆)Cl₂]₂, [Cp*RhCl₂]₂ or [Cp*IrCl₂]₂ to the ligand bridged bis‐amino acidate complexes [L_n(Cl)M–(OOC)(NH₂)CH–(CH₂)_nNH–CO]₂–C₆H₄ 11 – 14 .     

Behavior of α‐ and β‐cyclodextrin‐encapsulated allyl isothiocyanate as slow‐release additives in polylactide‐co‐polycaprolactone films

The natural antibacterial agent allyl isothiocyanate (AITC) encapsulated in either α‐ or β‐cyclodextrin (CD) has previously been evaluated as a slow‐release additive in polylactide‐co‐polycaprolactone (PLA–PCL) films designed for use in cheese packaging. In the research described in this article, thermogravimetric analysis (TGA) and thermogravimetric analysis in tandem with mass spectrometry (TGA–MS) were used to explore the thermal properties of CD‐encapsulated AITC complexes as well as those of PLA–PCL films containing these complexes. To our knowledge, this is the first reported application of the TGA–MS technique to explore the thermal stability of CD‐entrapped AITC and the first study to report differences in thermal stability of AITC in α‐and β‐CD cavities in the solid state. Observed differences in the thermal degradation profile of films containing the CD complexes can be explained if AITC binds more strongly to β‐CD than to α‐CD. This hypothesis has been reinforced by gas chromatography (GC) and high performance liquid chromatography (HPLC) studies, the results of which suggest that a new covalently bound AITC–CD complex may be formed when incorporating the β‐CD complex of AITC in PLA–PCL films but not when incorporating the α‐CD complex of AITC. This finding means that the α‐CD complex of AITC would be preferred in situations where adequate long‐term controlled release of AITC from polymer films is required, as for example in the case of active packaging applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Noels’ vs. Grubbs’ Catalysts: Evidence for One Unique Active Species for Two Different Systems!

The catalytically active propagating species involved in the self‐metathesis of ethyl oleate obtained from the multi‐component Noels’ catalytic system {[RuCl₂(p‐cymene)(PCy₃)]+Me₃SiCHN₂} are probably the same as those of the single‐component well‐defined Grubbs’ 1st generation catalyst, [Cl₂RuCHPh(PCy₃)₂] ( 1‐Ph ). In the case of the Noels’ catalyst, it involves the de‐coordination of p‐cymene, and the redistribution of PCy₃ ligands to generate only 5–10 % of [Cl₂RuCHR(PCy₃)₂], where R=CH (CH₂)₆ CH₃ ( 1‐Oct ) and R=CH (CH₂)₆ COOEt ( 1‐E ), while 1‐Ph can generate 100 % of these species.     

A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes

Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N₃P₃Cl₄[NH(CH₂)₃O], (1), and N₃P₃Cl₄[NH(CH₂)₃NMe], (2), were used to investigate a possible directing effect of the P-NHR moiety on the formation of products in the nucleophilic substitution reactions with diols such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimethyl-1,3-propanediol. The ³¹P NMR spectra of the reaction mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group.     

Impact of Sunflower (Helianthus annuus L.) Extracts Upon Reserve Mobilization and Energy Metabolism in Germinating Mustard (Sinapis alba L.) Seeds

One commonly observed effect of phytotoxic compounds is the inhibition or delay of germination of sensitive seeds. Mustard (Sinapis alba L.) seeds were incubated with aqueous extracts of sunflower (Helianthus annuus L.) leaves. Although sunflower phytotoxins did not influence seed viability, extracts completely inhibited seed germination. Inhibition of germination was associated with alterations in reserve mobilization and generation of energy in the catabolic phase of germination. Degradation of lipids was suppressed by sunflower foliar extracts resulting in insufficient carbohydrate supply. The lack of respiratory substrates and decrease in energy (ATP) generation resulted in suppression of the anabolic phase of seed germination and ultimately growth inhibition.Ewa Kupidłowska and Agnieszka Gniazdowska contributed equally to this work.     

Ionic polymers with expanded π‐conjugation systems derived from through‐space interaction in piperazinium and homopiperazinium rings

Reactions of N‐(2,4‐dinitrophenyl)‐4‐arylpyridinium chlorides (aryl (Ar) = phenyl and 4‐biphenyl) with piperazine or homopiperazine caused opening of the pyridinium ring and yielded polymers that consisted of 5‐piperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH₂CH₂)₂N⁺ (Cl^?)?CH? CH?C(Ar)? CH?CH? ) or 5‐homopiperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH₂CH₂CH₂)(CH₂CH₂)N⁺ (Cl^?)?CH? CH?C(Ar)? CH?CH? ) units. ¹H NMR spectral analysis suggested that the π‐electrons of the penta‐2,4‐dienylideneammonium group of the polymers were delocalized. UV‐visible spectral measurements revealed that the π‐conjugation system expanded along the polymer chains because of the orbital interaction between electrons of the two nitrogen atoms of the piperazinium and homopiperazinium rings. However, the π‐conjugation length depended on the distance between the two nitrogen atoms; that is, the polymers containing the piperazinium ring had a longer π‐conjugation length than those containing the homopiperazinium ring. Conversion of the piperazinium and homopiperazinium rings from the boat to the chair form led to a decrease in the π‐conjugation length. The surface of pellets that were molded from the polymers exhibited metallic luster, and these polymers underwent electrochemical oxidation in solution. Copyright © 2010 Society of Chemical Industry     

Phytotoxic Catechin Leached by Seeds of the Tropical Weed <Emphasis Type="Italic">Sesbania virgata</Emphasis>

Sesbania virgata (Cav.) Pers (wand riverhemp) is a fast-growing tropical legume species that has been used for revegetation of riparian forests and rehabilitation of degraded areas and that exhibits an invasive behavior in certain regions of Brazil. Preliminary studies have shown that seed leachates inhibit the germination and development of seedlings of some crop species. In this study, we report that the seed leachates of S. virgata inhibit the growth of Arabidopsis thaliana and rice. The flavonoid (+)-catechin is found in high amounts in these leachates. It was active at concentrations of 50 μg ml⁻¹, and its effect was not distinguishable from the (+)-catechin obtained from a commercial source. We found that (+)-catechin is located in the seed coat and is rapidly released in high concentrations (235 μg per seed) at the beginning of imbibition. Quercetin was also detected in the seed coat of S. virgata, but it was not released from the seeds. Other phytotoxic compounds in the seed leachates were also detected. The fact that S. virgata releases high amounts of (+)-catechin, which also has antimicrobial activity, and other phytotoxins from its seeds at the earliest stages of its development might represent some adaptative advantage to the seedling that contributes to its invasive behavior and successful establishment in different soils.     

A cross-linked conjugated metallopolymer comprised of bisaxially coordinated ruthenium tetra-t-butyl phthalocyanine connected by quaterthiophene linkers

A ruthenium tetra-t-butylphthalocyanine bisaxially ligated with 3,5-bis(2,2′-bithiophene-5-yl)pyridine was synthesized from ruthenium tetra-t-butylphthalocyanine dimer. The complex was electropolymerized (in CH₂Cl₂ and CH₃CN, with and without addition of BF₃·Et₂O) to yield an insoluble conjugated metallopolymer, which was characterized by cyclic voltammetry and UV–vis spectroelectrochemistry. The polymer combines the electrochemical and spectral properties of the phthalocyanine and of a polythiophene-type conjugated polymer. In the presence of BF₃, the polymer can be reversibly p-doped and de-doped. Materials obtained in CH₂Cl₂ (tested in the same solvent) and in CH₃CN/BF₃ (tested in CH₃CN) exhibit an unusual hysteresis of redox properties.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Responses of Flea Beetle <Emphasis Type="Italic">Phyllotreta cruciferae</Emphasis> to Synthetic Aggregation Pheromone Components and Host Plant Volatiles in Field Trials

Male-specific compounds, previously identified from Phyllotreta cruciferae and synthesized or isolated from natural sources, attracted both sexes of the beetle in field trials and therefore function as components of a male-produced aggregation pheromone. Six field experiments of 7 to 10 d duration each were conducted over 2 yr using modified boll weevil traps and two doses of pheromone. Treatments containing two doses of allyl isothiocyanate (AITC), a breakdown product of glucosinolates in Brassica napus L., a host plant of the beetles, were included in the study. A dose response was observed for both the pheromone components and AITC, and combinations of the pheromone and AITC generally attracted greater numbers of flea beetles than did either component itself. This increased attraction to a combination of beetle-produced compounds and host odors has not been previously demonstrated in halticine beetles and could help explain patterns of movement by P. cruciferae into field crops.     

Electrochemical polymerization of p‐terphenyl in mixed electrolyte of boron trifluoride diethyl etherate and CH2Cl2

High quality poly(p‐phenylene) (PPP) film with conductivity of 0.015 S cm^?1 was synthesized electrochemically by direct anodic oxidation of p‐terphenyl (PP) oligomers in boron trifluoride diethyl etherate (BFEE) containing 37.5% CH₂Cl₂ (v/v). The oxidation onset potential of PP in this medium was measured to be only 1.23 V vs. saturated calomel electrode (SCE), which was lower than that determined in CH₂Cl₂ + 0.1 mol L^?1 Bu₄NBF₄ (1.87 V vs. SCE). As‐formed PPP films showed good electrochemical behavior, good electrochromic property and good thermal stability. The structures and morphology of doped and dedoped PPP were investigated by UV‐vis, FTIR, and Scanning electron micrographs. The infrared spectroscopic measurements for the estimation of chain lengths revealed that PPP was composed of about 10 phenyl rings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010