Ecotoxicity studies reveal that organic cations in dicamba-derived ionic liquids can pose a greater environmental risk than the herbicide itself.

The following research provides novel and relevant insights into potential environmental consequences of combination of various organic cations with commercial systemic herbicide (dicamba), in accordance with a 'herbicidal ionic liquids' (HILs) strategy. Toxicity assays of five dicamba-based HILs comprising different hydrophobic and hydrophilic cations, namely choline [CHOL][DIC], ethyl betainate [BETC2][DIC], decyl betainate [BETC10][DIC], hexadecyl betainate [BETC16][DIC] and didecyldimethylammonium [DDA][DIC]), have been tested towards bacteria (Pseudomonas putida, Escherichia coli, Bacillus subtilis), algae (Chlorella vulgaris), fresh and marine water crustaceans (Daphnia magna, Artemia franciscana). The structure of respective substituents in the cation emerged as a decisive determinant of toxicity in the case of tested species. In consequence, small ions of natural origin ([CHOL] and [BETC2]) demonstrated toxicity numerous orders of magnitude lower compared to fully synthetic [DDA]. These results emphasize the role of cations' hydrophobicity, as well as origin, in the observed acute toxic effect. Time-dependent toxicity assays also indicated that betaine-type cations comprising an ester bond can rapidly transform into less harmful substances, which can generally result in a reduction in toxicity by even several orders of magnitude. Nonetheless, these findings challenge the concept of ionic liquids with herbicidal activity and give apparent parallels to adjuvant-dependent toxicity issues recently noted in typical herbicidal formulations.

Phytotoxic fungal secondary metabolites as herbicides.

Among the alternatives to synthetic plant protection products, biocontrol appears as a promising method. This review reports on the diversity of fungal secondary metabolites phytotoxic to weeds and on the approach generally used to extract, characterize, identify and exploit them for weed management. The 183 phytotoxic fungal secondary metabolites discussed in this review fall into five main classes of molecules: 61 polyketides, 53 terpenoids, 36 nitrogenous metabolites, 18 phenols and phenolic acids, and 15 miscellaneous. They are mainly produced by the genera Drechslera, Fusarium and Alternaria. The phytotoxic effects, more often described by the symptoms they produce on plants than by their mode of action, range from inhibition of germination to inhibition of root and vegetative growth, including tissue and organ alterations. The biochemical characterization of fungal secondary metabolites requires expertise and tools to carry out fungal cultivation and metabolite extraction, phytotoxicity tests, purification and fractionation of the extracts, and chemical identification procedures. Phytotoxicity tests are mainly carried out under controlled laboratory conditions (not always on whole plants), while effectiveness against targeted weeds and environmental impacts must be assessed in greenhouses and open fields. These steps are necessary for the formulation of effective, environment-friendly fungal secondary metabolites-derived bioherbicides using new technologies such as nanomaterials. © 2023 Society of Chemical Industry.

Potential of utilizing pathogen-derived mycotoxins as alternatives to synthetic herbicides in controlling the noxious invasive plant Xanthium italicum.

Discovery of environmentally friendly agents for controlling alien invasive species (AIS) is challenging and in urgent need as their expansion continues to increase. Xanthium italicum is a notorious invasive weed that has caused serious ecological and economic impacts worldwide. For the purpose of exploring the possibility of utilizing herbicidal mycotoxins to control this species, three compounds, a new compound, curvularioxide (1), a new naturally occurring compound, dehydroradicinin (2), and a known compound, radicinin (3), were isolated via activity-guided fractionation from the secondary metabolites of the pathogenic Curvularia inaequalis, which was found to infect X. italicum in natural habitats. All isolated compounds exhibited potent herbicidal activity on receiver species. It is noteworthy to mention that their effects on X. italicum in our bioassays were equivalent to the commercial herbicide glyphosate. Subsequent morphological analysis revealed that application of radicinin (3) severely hindered X. italicum seedlings' hypocotyl and root development. Malondialdehyde content and the activity of catalase and peroxidase of the seedlings were also significantly different from the control, implying the occurrence of induced oxidative stress. Our results suggest that pathogens infecting invasive plants might be valuable resources for developing safer herbicides for controlling weeds. © 2023 Society of Chemical Industry.

Kinetics of glyphosate and aminomethylphosphonic acid sorption onto montmorillonite clays in soil and their translocation to genetically modified corn.

The co-occurrence of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment and plants is a cause for concern due to potential threats to the ecosystem and human health. A major route of exposure is through contact with contaminated soil and consumption of crops containing GLP and AMPA residues. However, clay-based sorption strategies for mixtures of GLP and AMPA in soil, plants and garden produce have been very limited. In this study, in vitro soil and in vivo genetically modified corn models were used to establish the proof of concept that the inclusion of clay sorbents in contaminated soils will reduce the bioavailability of GLP and AMPA in soils and their adverse effects on plant growth. Effects of chemical concentration (1-10 mg/kg), sorbent dose (0.5%-3% in soil and 0.5%-1% in plants) and duration (up to 28 days) on sorption kinetics were studied. The time course results showed a continuous GLP degradation to AMPA. The inclusion of calcium montmorillonite (CM) and acid processed montmorillonite (APM) clays at all doses significantly and consistently reduced the bioavailability of both chemicals from soils to plant roots and leaves in a dose- and time-dependent manner without detectable dissociation. Plants treated with 0.5% and 1% APM inclusion showed the highest growth rate (p ≤ 0.05) and lowest chemical bioavailability with up to 76% reduction in roots and 57% reduction in leaves. Results indicated that montmorillonite clays could be added as soil supplements to reduce hazardous mixtures of GLP and AMPA in soils and plants.

Sorption of ionic liquids in soil enriched with polystyrene microplastic reveals independent behavior of cations and anions.

Recently, much attention has been focused on the application of the Ionic Liquids (ILs) with herbicidal activity in agriculture. It has been suggested that through the appropriate selection of cations and anions, one can adjust the properties of ILs, particularly the hydrophobicity, solubility, bioavailability, toxicity. In practical agricultural conditions, it will be beneficial to reduce the mobility of herbicidal anions, such as the commonly applied 2,4-dichlorophenoxyacetic acid [2,4-D] in the soil. Furthermore, microplastics are becoming increasingly prevalent in the soil, potentially stimulating herbicidal sorption. Therefore, we investigated whether cations in ILs influence the mobility of anions in OECD soil supplemented with polystyrene microplastic (PS). For this purpose, we used the 2,4-D based ILs consisting of: a hydrophilic choline cation [Chol][2,4-D] and a hydrophobic choline cation with a C12chain [C12Chol][2,4-D]. Characterization of selected micropolystyrene was carried out using the BET sorption-desorption isotherm, particle size distribution and changes in soil sorption parameters such as soil sorption capacity and cation exchange capacity. Based on the batch sorption experiment, the effect of microplastic on the sorption of individual cations and anions in soil contaminated with micropolystyrene was evaluated. The results obtained indicate that the introduction of a 1-10% (w/w) PS resulted in an 18-23% increase of the soil sorption capacity. However, the sorption of both ILs' cations increased only by 3-5%. No sorption of the [2,4-D] anion was noted. This suggests that cations and anions forming ILs, behave independently of each other in the environment. The results indicate the fact that ILs upon introduction into the environment are not a new type of emerging contaminant, but rather a typical mixture of ions. It is worth noting that when analyzing the behavior of ILs in the environment, it is necessary to follow the fate of both cations and anions.

Metabolomic Responses of Lettuce (Lactuca sativa) to Allelopathic Benzoquinones from Iris sanguinea Seeds.

Weed management is important in modern crop protection. Chemical weed control using synthetic herbicides, however, suffers from resistance and ecotoxicity. Metabolomic investigation of allelopathy (or allelochemicals) may provide novel alternatives to synthetic herbicides. This study aimed to investigate the detailed metabolomic responses of plants to allelochemicals in Iris seed extracts. The seed extracts of Iris sanguinea showed the strongest growth inhibitory activity against alfalfa, barnyard grass, lettuce, and mustard. 3-Hydroxyirisquinone (3-[10(Z)-heptadecenyl]-2-hydroxy-5-methoxy-1,4-benzoquinone) was isolated as a major allelochemical from I. sanguinea seeds through bioassay-guided fractionation. The compound inhibited the growth of shoots and roots by browning root tips. Discriminant analysis identified 33 differentially regulated lettuce metabolites after treatment with 3-hydroxyirisquinone (3HIQ). Metabolic pathway analysis revealed that several metabolic pathways, including aromatic amino acid biosynthesis and respiratory pathways, were affected by the compounds. Differential responses of membrane lipids (accumulation of unsaturated fatty acids) and extensive formation of reactive oxygen species were observed in root tissues following treatment with 3HIQ. Overall, alkylbenzoquinone from I. sanguinea induced extensive metabolic modulation, oxidative stress, and growth inhibition. The metabolomic responses to allelochemicals may provide fundamental information for the development of allelochemical-based herbicides.

Phytotoxic meroterpenoids with herbicidal activities from the phytopathogenic fungus Pseudopestalotiopsis theae.

The fungus Pseudopestalotiopsis theae isolated from the fresh leaves of Illigera celebica, has been reported to be a pathogenic fungus that can cause gray blight on tea leaves, a disease characterized by the appearance of necrotic lesions on tea leaves. The pathogenic substances in this fungus have not been clearly identified. Considering the possible involvement of specialized metabolites in symptom appearance, a chemical investigation of specialized metabolites on P. theae was conducted, resulting in the isolation of eight meroterpenoids, including six undescribed biscognienynes G-L and two known ones (biscognienynes B and D). The structures of these new compounds were characterized by extensive NMR spectroscopic and HR-ESI-MS data, and their absolute configurations were elucidated by ECD calculations. Except for biscogniyne L, all the isolated biscognienynes showed different degrees of phytotoxicity to tea in vivo, thereby revealing for the first time the substances in P. theae that cause tea gray blight. Inspired by the fact that phytotoxins produced by pathogenic fungus are an effective resource for designing natural and safe bioherbicides, when assayed the herbicidal activity through Petri dish bioassays, biscognienynes G-J showed phytotoxic effects against seed germination and seedling growth of Setaria viridis, strongly inhibiting seed germination percentage and radicle and germ lengths of seedlings. The results of this study demonstrated the great potential of biscognienynes G-J to be proposed and developed as ecofriendly herbicides.

Virtual screening based on pharmacophore model for developing novel HPPD inhibitors.

4-Hydroxyphenylpyruvate dioxygenase (HPPD) is an important target for herbicide design. A multilayered virtual screening workflow was constructed by combining two pharmacophore models based on ligand and crystal complexes, molecular docking, molecular dynamics (MD), and biological activity determination to identify novel small-molecule inhibitors of HPPD. About 110, 000 compounds of Bailingwei and traditional Chinese medicine databases were screened. Of these, 333 were analyzed through docking experiments. Five compounds were selected by analyzing the binding pattern of inhibitors with amino acid residues in the active pocket. All five compounds could produce stable coordination with cobalt ion, and form favorable π-π interactions. MD simulation demonstrated that Phe381 and Phe424 made large contributions to the strength of binding. The enzyme activity experiment verified that compound-139 displayed excellent potency against AtHPPD (IC50 = 0.742 µM), however, compound-5222 had inhibitory effect on human HPPD (IC50 = 6 nM). Compound-139 exhibited herbicidal activity to some extent on different gramineous weeds. This work provided a strong insight into the design and development of novel HPPD inhibitor using in silico techniques.

Specialized Metabolites from the Allelopathic Plant Retama raetam as Potential Biopesticides.

To cope with the rising food demand, modern agriculture practices are based on the indiscriminate use of agrochemicals. Although this strategy leads to a temporary solution, it also severely damages the environment, representing a risk to human health. A sustainable alternative to agrochemicals is the use of plant metabolites and plant-based pesticides, known to have minimal environmental impact compared to synthetic pesticides. Retama raetam is a shrub growing in Algeria's desert areas, where it is commonly used in traditional medicine because of its antiseptic and antipyretic properties. Furthermore, its allelopathic features can be exploited to effectively control phytopathogens in the agricultural field. In this study, six compounds belonging to isoflavones and flavones subgroups have been isolated from the R. raetam dichloromethane extract and identified using spectroscopic and optical methods as alpinumisoflavone, hydroxyalpinumisoflavone, laburnetin, licoflavone C, retamasin B, and ephedroidin. Their antifungal activity was evaluated against the fungal phytopathogen Stemphylium vesicarium using a growth inhibition bioassay on PDA plates. Interestingly, the flavonoid laburnetin, the most active metabolite, displayed an inhibitory activity comparable to that exerted by the synthetic fungicide pentachloronitrobenzene, in a ten-fold lower concentration. The allelopathic activity of R. raetam metabolites against parasitic weeds was also investigated using two independent parasitic weed bioassays to discover potential activities on either suicidal stimulation or radicle growth inhibition of broomrapes. In this latter bioassay, ephedroidin strongly inhibited the growth of Orobanche cumana radicles and, therefore, can be proposed as a natural herbicide.

The impact of aqueous and N-hexane extracts of three Fabaceae species on seed germination and seedling growth of some broadleaved weed species.

Weed infestation is a persistent problem for centuries and continues to be major yield reducing issue in modern agriculture. Chemical weed control through herbicides results in numerous ecological, environmental, and health-related issues. Moreover, numerous herbicides have evolved resistance against available herbicides. Plant extracts are regarded as an alternative to herbicides and a good weed management option. The use of plant extracts is environmentally safe and could solve the problem of herbicide resistance. Therefore, laboratory and wire house experiments were conducted to evaluate the phytotoxic potential of three Fabaceae species, i.e., Cassia occidentalis L. (Coffee senna), Sesbania sesban (L.) Merr. (Common sesban) and Melilotus alba Medik. (White sweetclover) against seed germination and seedling growth of some broadleaved weed species. Firstly, N-hexane and aqueous extracts of these species were assessed for their phytotoxic effect against lettuce (Lactuca sativa L.). The extracts found more potent were further tested against germination and seedling growth of four broadleaved weed species, i.e., Parthenium hysterophorus L. (Santa-Maria), Trianthema portulacastrum L. (Pigweed), Melilotus indica L (Indian sweetclover). and Rumex dentatus L. (Toothed dock) in Petri dish and pot experiments. Aqueous extracts of all species were more toxic than their N-hexane forms for seed germination and seedling growth of lettuce; therefore, aqueous extracts were assessed for their phytotoxic potential against four broadleaved weed species. Aqueous extracts of all species proved phytotoxic against T. portulacastrum, P. hysterophorus, M. indica and R. dentatus and retarder their germination by 57, 90, 100 and 58%, respectively. Nevertheless, foliar spray of C. occidentalis extract was the most effective against T. portulacastrum as it reduced its dry biomass by 72%, while M. alba was effective against P. hysterophorus, R. dentatus and M. indica and reduced their dry biomass by 55, 68 and 81%, respectively. It is concluded that aqueous extracts of M. alba, S. sesban and C. occidentalis could be used to retard seed germination of T. portulacastrum, P. hysterophorus, M. indica and R. dentatus. Similarly, aqueous extracts of C. occidentalis can be used to suppress dry biomass of T. portulacastrum, and those of M. alba against P. hysterophorus, R. dentatus. However, use of these extracts needs their thorough testing under field conditions.

Evaluation of Pomelo Seed Extracts as Natural Antioxidant, Antibacterial, Herbicidal Agents, and Their Functional Components.

Pomelo seeds (PS) are important by-product of pomelo fruits (Citrus grandis Osbeck). The value-added utilization of PS remains highly challenged. This study aimed to investigate the utilization potential of PS as natural antioxidant, antibacterial, herbicidal agents, and their functional components. The ethanolic extract (EE) of PS and its four fractions as PEE (petroleum ether extract), AcOEtE (ethyl acetate extract), BTE (butanol extract), and WE (water extract), were prepared and biologically evaluated. BTE exhibited the best antioxidant activity among all these extracts, in both ABTS (2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt) and FRAP (ferric reducing antioxidant power) assays. AcOEtE was superior to other extracts in herbicidal assay against both Festuca elata Keng (IC50 of 0.48 mg mL-1 ) and Amaranthus retroflexus L. (IC50 of 0.94 mg mL-1 ). Meanwhile, both AcOEtE and BTE demonstrated inhibitory effects against Bacillus subtilis, Escherichia coli, and Xanthomonas citri subsp. citri, with MIC ranging 2.5-5.0 mg mL-1 . Furthermore, the primary chemical components involving naringin, deacetylnomilin, limonin, nomilin, and obacunone, were quantified in all these extracts. PCA (principal component analysis) suggested that naringin might highly contribute to the antioxidant activity of PS, and the herbicidal activity should be ascribed to limonoids. This study successfully identified AcOEtE and BTE as naturally occurring antioxidant, antibacterial, and herbicidal agents, showing application potential in food and cosmetics industries, and organic farming agriculture.

Bioactive Diterpenes from the Brazilian Native Plant (Moquiniastrum pulchrum) and Their Application in Weed Control.

Even today, weeds continue to be a considerable problem for agriculture. The application of synthetic herbicides produces serious environmental consequences, and crops suffer loss of their activity due to the appearance of new resistant weed biotypes. Our aim is to develop new effective natural herbicides that improve the problem of resistance and do not harm the environment. This work is focused on a bioassay-guided isolation and the characterization of natural products present in Moquiniastrum pulchrum leaves with phytotoxic activity and its preliminary application in weeds. Moquiniastrum pulchrum was selected for two reasons: it is an abundant species in the Cerrado region (the second most important ecosystem in Brazil, after the Amazon)-the explanation behind its being a dominant species is a major focus of interest-and it has traditional employment in folk medicine. Six major compounds were isolated in this plant: one flavone and five diterpenes, two of which are described for the first time in the literature. Four of the six compounds exhibited phytotoxic activity in the bioassays performed. The results confirmed the phytotoxic potential of this plant, which had not been investigated until now.

Anti-Enterococcus Faecalis, Cytotoxicity, Phytotoxicity, and Anticancer Studies on Clausena excavata Burum. f. (Rutaceae) Leaves.

BACKGROUND: Clausena excavata Burum. f. has long been applied in ethnomedicine for the treatment of various disorders like rhinitis, headache, cough, wound healing, fever, and detoxification. This study is aimed at investigating the antibacterial activity against Enterococcus faecalis ATCC 49532 using AlamarBlue assay and atomic force microscopy (AFM) as well as the cytotoxicity, anticancer, and phytotoxicity of C. excavata. METHOD: Bacterial cell viability was performed by using microplate AlamarBlue assay. Atomic force microscopy was used to determine morphological changes in the surface of bacterial cells. Cytotoxicity and phytotoxicity were determined by brine shrimp lethality and Lemna minor bioassay. Caco-2 (colorectal adenocarcinoma) cell line was used for the evaluation of the anticancer effects. RESULT: Among the fractions tested, ethyl acetate (EA) fraction was found to be active with minimum inhibitory concentration (MIC) of 750 µg/mL against E. faecalis, but other fractions were found to be insensitive to bacterial growth. Microscopically, the EA fraction-treated bacteria showed highly damaged cells with their cytoplasmic content scattered all over. The LC50 value of the EA fraction against brine shrimp was more than 1000 µg/mL showing the nontoxic nature of this fraction. Chloroform (CH), EA, and methanol (MOH) fractions of C. excavata were highly herbicidal at the concentration of 1000 µg/mL. EA inhibited Caco-2 cell line with an IC50 of 20 µg/mL. CONCLUSIONS: This study is the first to reveal anti-E. faecalis property of EA fraction of C. excavata leaves, natural herbicidal, and anticancer agents thus highlight the potential compound present in its leaf which needs to be isolated and tested against multidrug-resistant E. faecalis.

Allelopathic activity of some Sri Lankan seaweed extracts and the isolation of a new brominated nonaromatic isolaurene type sesquiterpene from red alga Laurencia heteroclada harvey.

This study investigated the allelopathic activity of sixteen seaweed extracts using lettuce seed germination bioassay. The results of the preliminary investigation suggested that the methanol extracts of seven seaweeds demonstrated significant properties inhibitory to seed germination. In addition, chemical investigation of an active extract of the alleopathic Laurencia heteroclada Harvey led to the isolation of four known compounds as well as a new brominated nonaromatic isolaurene type sesquiterpene. The structural elucidation of pure compounds was carried out using spectroscopic methods and by comparison with literature. As seaweeds are highly abundant around Sri Lanka, they could be developed as an ecofriendly natural herbicide in their crude form.

Development of pre-emergence herbicide based on Arabic gum-gelatin, apple pectin and savory essential oil nano-particles: A potential green alternative to metribuzin.

This study was conducted as a plot experiment to investigate the phytotoxicity effects of nano-encapsulated savory essential oil (EO) when it is incorporated separately into carbohydrate and protein natural polymers (Arabic gum-gelatin, apple pectin and gelatin) and two cross-linkers including one poly acid and one enzyme (citric acid and transglutaminase enzyme). Each product was tested as a pre-emergence herbicide against amaranth and tomato. The evaluations also involved determining the stability, morphology, encapsulation efficiency and release properties of the prepared formulations. Coating the savory EO with cross-linked biopolymers enhanced its stability and herbicidal activity, compared to the EO nano-emulsion without any polymer or cross-linker. Among the tested formulations, the strongest inhibitory effect against amaranth germination and growth was caused by Arabic gum-gelatin and apple pectin biopolymers at the concentration of 3 ml/L of EO, when cross-linked with citric acid. These two treatments had slight effects on tomato seedlings, however. The suppressive ability of the formulations was almost similar and comparable to the chemical herbicide metribuzin (1.75 g/L). In conclusion, Arabic gum-gelatin and apple pectin cross-linked by citric acid containing savory EO can be considered as potential, green and safe replacements for metribuzin in organic tomato production.

Physicochemical properties, droplet size and volatility of dicamba with herbicides and adjuvants on tank-mixture.

The adoption of dicamba-tolerant soybean varieties has increased the concern and demand for new drift and volatility reduction technologies. Potential spray nozzles and adjuvants should be studied to determine its effects on drift and volatility of dicamba tank-mixtures. The objective of this study was to evaluate physicochemical characteristics of spray solutions containing dicamba; to analyze droplet size effect with air induction nozzles; and to assess dicamba volatilization on soybean plants with a proposed methodology. Treatments included dicamba only and mixtures with herbicides and adjuvants. Dicamba mixed with lecithin + methyl soybean oil + ethoxylated alcohol adjuvant had the greatest efficacy potential among treatments considering tank-mixture pH, surface tension, contact angle and droplet size. The MUG11003 nozzle produced the coarsest droplet size and was better suited for drift management among nozzle types. The proposed volatilization methodology successfully indicated dicamba volatilization in exposed soybean plants and among the evaluated treatments, it showed greater volatilization for dicamba with glyphosate + lecithin + propionic acid adjuvant.

Nutrients Supplementation through Organic Manures Influence the Growth of Weeds and Maize Productivity.

Declining rate of productivity and environmental sustainability is forcing growers to use organic manures as a source of nutrient supplement in maize farming. However, weed is a major constraint to maize production. A field study was carried out over two seasons to evaluate various integrated nutrient and weed management practices in hybrid maize. The treatment combinations comprised of supplementation of inorganic fertilizer (25% nitrogen) through bulky (Farmyard manure and vermicompost) and concentrated (Brassicaceous seed meal (BSM) and neem cake (NC)) organic manures and different mode of weed management practices like chemical (atrazine 1000 g ha-1) and integrated approach (atrazine 1000 g ha-1 followed by mechanical weeding). Repeated supplementation of nitrogen through concentrated organic manures reduced the density and biomass accumulation of most dominant weed species, Anagalis arvensis by releasing allelochemicals into the soil. But organic manures had no significant impact on restricting the growth of bold seeded weeds like Vicia hirsuta and weed propagated through tubers i.e., Cyperus rotundus in maize. By restricting the weed growth and nutrient removal by most dominating weeds, application of BSM enhanced the growth and yield of maize crop. Repeated addition of organic manures (BSM) enhanced the maize grain yield by 19% over sole chemical fertilizer in the second year of study. Application of atrazine as pre-emergence (PRE) herbicide significantly reduced the density of A. arvensis, whereas integration of mechanical weeding following herbicide controlled those weeds which were not usually controlled with the application of atrazine. As a result, atrazine at PRE followed by mechanical weeding produced the highest maize grain yield 6.81 and 7.10 t/ha in the first year and second year of study, respectively.

Auxinic herbicide conjugates with an α-amino acid function: Structural requirements for biological activity on motor cells.

Two Fabaceae exhibiting rapid osmocontractile pulvinar movements were used in this study because this activity is modified by natural auxin and dramatically by 2,4D. A short chain with a carboxylic group being required for auxinic properties, a critical point to analyze is whether the recently synthesized proherbicide ε-(2,4-dichlorophenoxyacetyl)-L-Lys (2-4D-L-Lys) maintains some biological activity despite the increase in length of the chain and the substitution of the carboxyl group by an α-amino acid function. No trace of 2,4D could be detected in the pulvinar tissues treated for 1 h with 2,4D-L-Lys. Complementary approaches (electrophysiology, pH measurements, use of plasma membrane vesicles) suggest that it was less efficient than 2,4D to activate the plasma membrane H+-ATPase (PM-H+-ATPase). However, it modified the various ion-driven reactions of Mimosa pudica and Cassia fasciculata pulvini in a similar way as 2,4D. Additionally, it was much more effective than fusicoccin to inhibit seismonastic movements of M. pudica leaves and, at low concentrations, to promote leaflet opening in dark, indicating that its mode of action is more complex than the only activation of the PM-H+-ATPase. Various substitutions on 2,4D-L-Lys affected its activity in correlation with the molecular descriptor "halogen ratio" of these derivatives. Conjugation with D-Lys also led to a decrease of pulvinar reaction, suggesting that 2,4D-Lys maintains the main signaling properties of 2,4D involved in pulvinar movements providing that the terminal zwitterion is in a suitable orientation. Our data guide future investigations on the effect of 2,4D and 2,4D-L-Lys on the vacuolar pump activity of motor cells.

Pennelliisides A-C, 2,3,4-Trisubstituted Acyl Glucoses Isolated from Solanum pennellii.

Solanum species accumulate a variety of secondary metabolites in their trichomes, and it is well known that acyl sugars are specialized metabolites secreted by the trichomes. However, very few reports provide detailed information on the chemical structure of polyacylated glucose derivatives, due to the α and ß isomerization that can occur at the C-1 position. In this study, a strategy was established to isolate polyacylated glucose derivatives. According to the developed strategy, hydroxy groups were derivatized to a benzyloxy group using TriBOT. After isolation of the compounds in pure form and deprotection of the benzyloxy group, the chemical structures of pennelliisides A-C were determined as 2,3,4-O-triisobutyryl-d-glucose, 3-O-(8-methylnonanoyl)-2,4-O-diisobutyryl-d-glucose, and 3-O-decanoyl-2,4-O-diisobutyryl-d-glucose, respectively. Structural elucidation was performed using spectroscopic techniques, including 1D and 2D NMR, FD-MS, and GC-MS. It was also found that the fatty acid moiety contributes to the allelopathic properties of the isolated compounds.

Novel lipophilic analogues from 2,4-D and Propanil herbicides: Biological activity and kinetic studies.

This work describes the synthesis of new lipophilic amides and esters analogues of classical organochlorides herbicides by incorporation of long-chains from fatty acids and derivatives. The new fatty esters and amides were synthesized in 96-99% and 80-89% yields, respectively. In general, all compounds tested showed superior in vitro activity than commercial herbicides against growth L. sativa and A. cepa, in ranges 86-100% of germinative inhibition. The target compounds showed, significantly more susceptible towards acid hydrolysis than 2,4-dichlorophenoxyacetic acid (2,4-D). The kinetic and NMR studies showed that the incorporation of lipophilic chains resulted in a decrease in half-life time of new herbicides compounds (1.5 h) than 2,4-D (3 h). These findings suggest the synthesis of new lipophilic herbicides as potential alternative to traditional formulations, by incorporation of long fatty alkyl chains in the molecular structure of 2,4-D, resulting in superior in vitro herbicidal activity, best degradation behavior and more hydrophobic derivatives.