Similarities on the mode of action of the terpenoids citral and farnesene in Arabidopsis seedlings involve interactions with DNA binding proteins.

The sesquiterpene farnesene and the monoterpene citral are phytotoxic natural compounds characterized by a high similarity in macroscopic effects, suggesting an equal or similar mechanism of action when assayed at IC50 concentration. In the present study, a short-time experiment (24 and 48 h) using an imaging spectrofluorometer allowed us to monitor the in-vivo effects of the two molecules, highlighting that both terpenoids were similarly affecting all PSII parameters, even when the effects of citral were quicker in appearing than those of farnesene. The multivariate, univariate, and pathway analyses, carried out on untargeted-metabolomic data, confirmed a clear separation of the plant metabolome in response to the two treatments, whereas similarity in the affected pathways was observed. The main metabolites affected were amino acids and polyamine, which significantly accumulated in response to both treatments. On the contrary, a reduction in sugar content (i.e. glucose and sucrose) was observed. Finally, the in-silico studies demonstrated a similar mechanism of action for both molecules by interacting with DNA binding proteins, although differences concerning the affinity with the proteins with which they could potentially interact were also highlighted. Despite the similarities in macroscopic effects of these two molecules, the metabolomic and in-silico data suggest that both terpenoids share a similar but not equal mechanism of action and that the similar effects observed on the photosynthetic machinery are more imputable to a side effect of molecules-induced oxidative stress.

Comparative Analysis of Tolerance to Salt Stress and Water Deficit in Two Invasive Weeds of the Genus Erigeron (Asteraceae).

Erigeron bonariensis and E. sumatrensis are two noxious weeds present in many parts of the world. Their tolerance to salinity and water deficit was analysed at the seed germination stage and during vegetative development. Seed germination was tested in solutions with different concentrations of NaCl and polyethylene glycol (PEG). Growth parameters, photosynthetic pigments, ion accumulation, and antioxidant mechanisms were analysed in plants that were subjected to increasing NaCl solutions, or severe water deficit by completely restricting irrigation. Seed germination was mostly affected by NaCl, but less by PEG in both species. E. bonariensis had a faster germination in all treatments and maintained a higher percentage of germination under the highest concentration of salt applied. Growth responses were similar in the two species, both being more affected by higher salt concentrations than by water deficit. The main differences in the responses of the two species to stress regard K+ and proline concentration. K+ in roots decreased under salt stress in E. sumatrensis, but remained constant in leaves, whereas in E. bonariensis increased in roots and leaves in salt-stressed plants. Proline concentration increased in all E. bonariensis plants under salt stress, but only in those under the highest salt concentration in E. sumatrensis. The results obtained indicate that the two species are relatively tolerant to water deficit and medium salinity but are susceptible to high NaCl concentrations.

Mechanistic Aspects and Effects of Selected Tank-Mix Partners on Herbicidal Activity of a Novel Fatty Acid Ester.

Only a limited number of contact herbicides exist in agricultural production. While systemic herbicides are more efficient also at suboptimum spray coverage with long-lasting weed control, contact herbicides provide several advantages. There is no translocation to fruits or roots of plantation and other crop, low risk for resistance development, and minor risk for spray-drift damage. Besides, synthetic products that often have toxicological or residues issues, natural fatty acids, particularly pelargonic acid (PA), have contact activity and are safer for home and garden use. We recently described a methyl capped polyethylene glycol ester of pelargonic acid (PA-MPEG) that acts independent of acid formation. Both, PA-MPEG and PA are applied at high rates per hectare to achieve excellent weed control. Here, we report about potential additives to increase PA-MPEG efficacy. The herbicidal active, 1-decanol, and the non-phytotoxic alkylated seed oil-based adjuvant, HastenTM, improved performance and outperformed a commercial PA herbicide. Both, PA-MPEG and PA appear to mainly act by the disintegration of bio-membranes besides having effects on transpiration. The main suggested effect is desiccation due to cutting the water continuum at the site of evaporation in the intercellular spaces. The synergistic action of the adjuvant HastenTM and its practical uses are also discussed.

Capped polyethylene glycol esters of fatty acids as novel active principles for weed control.

BACKGROUND: Ever since the beginning of agriculture, yields have been threatened by weeds. Chemical weed control is far more effective and economical than other methods. The frequent use of herbicides has led to environmental and human health concerns, resulting in the banning of several herbicides and challenges for the future of important active compounds such as glyphosate. RESULTS: The herbicidal activity of sustainable alternatives based on certain esters of fatty acids (FA), the action of which is unrelated to the free acid, on common weeds is assessed and reported. The 13 derivatives of FA showed better physicochemical properties than pelargonic acid-based herbicides. All the reported compounds have phytotoxic activity, the highest efficacy being displayed by the methyl end-capped polyethylene glycol (mPEG) ester of pelargonic acid having 6EO (ethylene oxide). This mPEG ester showed equal or better phytotoxicity than the pelargonic acid benchmark at reduced application rate and spray volume. The active compound is a liquid at ambient temperatures, has no bad smell and is not volatile, in contrast to pelargonic acid. Notably, this active compound can be the final product, can be sprayed without adjuvants and is relatively easy to co-formulate. CONCLUSION: A new lead substance is presented that is a sustainable alternative to current contact herbicides. In particular, it has potential application on railways, in precision agriculture and as a harvest aid. Its good performance and technical properties suggest this mPEG ester group may also overcome the volatility-related problems of other organic acids such as auxins. © 2021 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Phytotoxic Effects and Mechanism of Action of Essential Oils and Terpenoids.

Weeds are one of the major constraints in crop production affecting both yield and quality. The excessive and exclusive use of synthetic herbicides for their management is increasing the development of herbicide-resistant weeds and is provoking risks for the environment and human health. Therefore, the development of new herbicides with multitarget-site activity, new modes of action and low impact on the environment and health are badly needed. The study of plant-plant interactions through the release of secondary metabolites could be a starting point for the identification of new molecules with herbicidal activity. Essential oils (EOs) and their components, mainly terpenoids, as pure natural compounds or in mixtures, because of their structural diversity and strong phytotoxic activity, could be good candidates for the development of new bioherbicides or could serve as a basis for the development of new natural-like low impact synthetic herbicides. EOs and terpenoids have been largely studied for their phytotoxicity and several evidences on their modes of action have been highlighted in the last decades through the use of integrated approaches. The review is focused on the knowledge concerning the phytotoxicity of these molecules, their putative target, as well as their potential mode of action.

Phytotoxic Activity of the Natural Compound Norharmane on Crops, Weeds and Model Plants.

Norharmane is a secondary metabolite that appears in different species of land plants. In this paper, we investigated for the first time the specificity of norharmane through germination and growth tests on some crops as Zeamays L. (maize), Triticumaestivum L. (wheat), Oryza sativa L. (rice) and Lactucasativa L. (lettuce) and weeds as Amaranthusretroflexus L. (amaranth), Echinochloacrus-galli L. (barnyard grass), Plantago lanceolata L. (ribwort), Portulaca oleracea L. (common purslane) and Avenafatua L. (wild oat), and its phytotoxic capacity on the metabolism of adult Arabidopsis thaliana L. (thale cress) by measuring chlorophyll a fluorescence, pigment content, total proteins, osmotic potential and morphological analysis. Norharmane had an inhibitory effect on the germination of A.fatua and P.lanceolata, and the growth of P.oleracea, E.crus-galli and A.retroflexus. On adult A. thaliana plants, the compound was more effective to watering, leading to water stress that compromised the growth of the plants and ultimately affected the photosynthetic apparatus. Therefore, this research shows that norharmane not only affects seedlings' metabolism, but also damages the metabolism of adult plants and can be a potential model for a future bioherbicide given its specificity.

Potential Effects of Essential Oils Extracted from Mediterranean Aromatic Plants on Target Weeds and Soil Microorganisms.

Essential oils (EOs), extracted from aromatic plants, have been proposed as candidates to develop natural herbicides. This study aimed to evaluate the herbicidal potential of Thymbra capitata (L.) Cav., Mentha × piperita L. and Santolina chamaecyparissus L. essential oils (EOs) on Avena fatua L., Echinochloa crus-galli (L.) P. Beauv, Portulaca oleracea L. and Amaranthus retroflexus L. and their effects on soil microorganisms. A pot experiment was set up and three EOs at three doses were applied by irrigation. Efficacy and effects of EOs on weed growth were determined. Soil microbial biomass carbon and nitrogen, microbial respiration, and the main microbial groups were determined at days 7, 28 and 56. EOs demonstrated herbicidal activity, increasing their toxicity with the dose. T. capitata was the most effective against all weeds at the maximum dose. P. oleracea was the most resistant weed. Soil microorganisms, after a transient upheaval period induced by the addition of EOs, recovered their initial function and biomass. T. capitata EO at the highest dose did not allow soil microorganisms to recover their initial functionality. EOs exhibited great potential as natural herbicides but the optimum dose of application must be identified to control weeds and not negatively affect soil microorganisms.

Cherry tomato and persimmon kaki conservation with a natural and biodegradable film.

The chemical composition of Essential Oils Satureja montana and Mentha longifolia was determined, and their activity against important phytopathogenic and post-harvest fungi was studied, to evaluate their potential as natural food preservatives. The major compounds were carvacrol (24.0%), γ-terpinene (15.9%) and p-cymene (14.2%) in S. montana, and piperitenone oxide (52.7%) and piperitone oxide (23.5%) in M. longifolia. EOs were tested in vitro on Alternaria alternata, Botryotinia fuckeliana, Curvularia hawaiiensis, Fusarium equiseti, F. oxysporum lycopersici, Rhizoctonia solani and Verticillium dahliae. S. montana demonstrated excellent results. At 300 µg mL-1 the growth of all fungi was inhibited with 100% mycelial growth inhibition (MGI), except for B. fuckeliana (92%). M. longifolia was less effective, and its best result was against Verticillium dahliae (100% MGI) at 400 and 300 µg mL-1. S. montana EO was selected for in vivo antifungal tests in Cherry tomatoes and kaki "Persimmon" against A. alternata. The S. montana EO biofilm reduced post-harvest fungi development. In tomato, it inhibited up to 90% after 20 days. Necrosis did not occur for 2 months in the persimmon fruits. S. montana EO is an effective non-toxic preservative that can be considered to develop a botanical and enviro-friendly low-risk biofungicide.

Herbicidal Activity of Thymbra capitata (L.) Cav. Essential Oil.

The bioherbicidal potential of Thymbra capitata (L.) Cav. essential oil (EO) and its main compound carvacrol was investigated. In in vitro assays, the EO blocked the germination and seedling growth of Erigeron canadensis L., Sonchus oleraceus (L.) L., and Chenopodium album L. at 0.125 µL/mL, of Setaria verticillata (L.) P.Beauv., Avena fatua L., and Solanum nigrum L. at 0.5 µL/mL, of Amaranthus retroflexus L. at 1 µL/mL and of Portulaca oleracea L., and Echinochloa crus-galli (L.) P.Beauv. at 2 µL/mL. Under greenhouse conditions, T. capitata EO was tested towards the emergent weeds from a soil seedbank in pre and post emergence, showing strong herbicidal potential in both assays at 4 µL/mL. In addition, T. capitata EO, applied by spraying, was tested against P. oleracea, A. fatua and E. crus-galli. The species showed different sensibility to the EO, being E. crus-galli the most resistant. Experiments were performed against A. fatua testing T. capitata EO and carvacrol applied by spraying or by irrigation. It was verified that the EO was more active at the same doses in monocotyledons applied by irrigation and in dicotyledons applied by spraying. Carvacrol effects on Arabidopsis root morphology were also studied.

Control of Erigeron bonariensis with Thymbra capitata, Mentha piperita, Eucalyptus camaldulensis, and Santolina chamaecyparissus Essential Oils.

In the search of sustainable and environmentally friendly methods for weed control, there is increasing interest in essential oils (EOs) as an approach to reduce synthetic herbicide use. The phytotoxicity of Thymbra capitata, Mentha piperita, Eucalyptus camaldulensis, and Santolina chamaecyparissus EOs against the noxious weed Erigeron bonariensis were evaluated in pre- and post-emergence assays in greenhouse conditions. The EOs were applied at 2, 4, and 8 µL/mL, with Fitoil used as emulsifier. In post-emergence, two ways of application were tested, irrigation and spraying. Several germination parameters (germination %, mean germination time, and synchrony of the germination process) were evaluated in pre-emergence tests, and the phytotoxicity level was assessed in post-emergence. In pre-emergence, all EOs significantly reduced seed germination as compared to the controls, ranking: T. capitata > E. camaldulensis > S. chamaecyparissus > M. piperita. The effectiveness of all EOs varied with the tested dose, always following the rank 2 µL < 4 µL < 8 µL, with T. capitata EO showing full effectiveness even at the lowest dose. In post-emergence, T. capitata was the most effective EO, inducing a rather complete inhibition of plantlet growth at the highest two doses. These EOs demonstrated to have good potential for the formulation of natural herbicides.

Insights on Salt Tolerance of Two Endemic Limonium Species from Spain.

We have analysed the salt tolerance of two endemic halophytes of the genus Limonium, with high conservation value. In the present study, seed germination and growth parameters as well as different biomarkers-photosynthetic pigments, mono and divalent ion contents-associated to salt stress were evaluated in response to high levels of NaCl. The study was completed with an untargeted metabolomics analysis of the primary compounds including carbohydrates, phosphoric and organic acids, and amino acids, identified by using a gas chromatography and mass spectrometry platform. Limonium albuferae proved to be more salt-tolerant than L. doufourii, both at the germination stage and during vegetative growth. The degradation of photosynthetic pigments and the increase of Na+/K+ ratio under salt stress were more accentuated in the less tolerant second species. The metabolomics analysis unravelled several differences between the two species. The higher salt tolerance of L. albuferae may rely on its specific accumulation of fructose and glucose under high salinity conditions, the first considered as a major osmolyte in this genus. In addition, L. albuferae showed steady levels of citric and malic acids, whereas the glutamate family pathway was strongly activated under stress in both species, leading to the accumulation of proline (Pro) and γ-aminobutyric acid (GABA).

Qualitative and Quantitative Differences in Osmolytes Accumulation and Antioxidant Activities in Response to Water Deficit in Four Mediterranean Limonium Species.

Limonium is a genus represented in the Iberian Peninsula by numerous halophytic species that are affected in nature by salinity, and often by prolonged drought episodes. Responses to water deficit have been studied in four Mediterranean Limonium species, previously investigated regarding salt tolerance mechanisms. The levels of biochemical markers, associated with specific responses-photosynthetic pigments, mono- and divalent ions, osmolytes, antioxidant compounds and enzymes-were determined in the control and water-stressed plants, and correlated with their relative degree of stress-induced growth inhibition. All the tested Limonium taxa are relatively resistant to drought on the basis of both the constitutive presence of high leaf ion levels that contribute to osmotic adjustment, and the stress-induced accumulation of osmolytes and increased activity of antioxidant enzymes, albeit with different qualitative and quantitative induction patterns. Limonium santapolense activated the strongest responses and clearly differed from Limonium virgatum, Limonium girardianum, and Limonium narbonense, as indicated by cluster and principal component analysis (PCA) analyses in agreement with its drier natural habitat, and compared to that of the other plants. Somewhat surprisingly, however, L. santapolense was the species most affected by water deficit in growth inhibition terms, which suggests the existence of additional mechanisms of defense operating in the field that cannot be mimicked in greenhouses.

Chemical Composition, Herbicidal and Antifungal Activity of Satureja cuneifolia Essential Oils from Spain.

The chemical composition of essential oils from Satureja cuneifolia growing in east Spain was analyzed by GC, GC/MS. Forty-five compounds accounting for 99.1% of the total oil were identified. Camphor (47.6%), followed by camphene (13.6%) were the main compounds. Their herbicidal and antifungal activity was tested in vitro against three weeds (Amaranthus hybridus, Portulaca oleracea and Conyza canadensis) and eleven common pathogenic or saprophytic fungi (Phytophthora citrophthora, P. palmivora, Pythium litorale, Verticillium dahlia, Rhizoctonia solani, Penicillium hirsutum, Colletotrichum gloeosporioides, Phaeoacremonium aleophilum, Phaemoniella chlamydospora, Cylindrocarpon liriodendri and C. macrodidymum). The essential oil was very active against A. hybridus and C. canadensis significantly inhibiting their germination and seedling growth. Minor activity was shown against P. oleracea, depending on the concentration applied. P. palmivora, P. citrophthora and Pa. chlamydospora were the most sensitive fungi to the treatment with the essential oil, whereas R. solani showed no inhibition. Results showed that S. cuneifolia essential oil could be used for biocontrol of weeds and fungal plant diseases.

Chemical composition of the essential oil of Zingiber zerumbet var. darcyi.

The chemical composition of essential oil obtained by hydrodistillation method from the rhizomes of Z. zerumbet var. darcyi was determined by GC and GC-MS. Thirty-three compounds, accounting for 93.6% of the oil were identified including twenty compounds in minor (0.1-0.6%) and eight in trace (<0.05%) amounts. The main compounds were zerumbone (69.9%) alpha-humulene (12.9%), humulene epoxide II (2.5%), caryophyllene oxide (1.1%) and camphene (1.9%). In this analysis, it has been found that the variety could be used as an additional new source of natural zerumbone besides Zingiber zerumbet. This is a first report on the analysis of Z. zerumbet var. darcyi oil.

Chemical variability in the essential oil of Cinnamomum tamala L. leaves from India.

The chemical composition of the essential oils obtained from the fresh leaves of Cinnamomum tamala Nees et Eberm. was determined by GC and GC-MS. The yield of the oil on a dry weight basis ranged from 1.2% to 3.9% (w/w). Phenyl propanoids constitute the major portion (88.9-95.0%) of the oils. Fifty-four compounds were identified from the oils. Eugenol (91.4-41.8%) was the main compound, followed by eugenyl acetate (0.0-47.1%) and α-phellandrene (0.6-2.5%) in the analysed oils.

Chemical composition and herbicidal activity of the essential oil from a Cistus ladanifer L. population from Spain.

The essential oil composition of Cistus ladanifer grown in central Spain was analysed by gas chromatography and gas chromatography/mass spectrometry, revealing it to be rich in oxygenated compounds, with trans-pinocarveol (20.00%), bornyl acetate (7.03%) and terpinen-4-ol (6.37%) as the main monoterpene compounds. Viridiflorol (13.59%) and ledol (4.36%) were the main constituents of the oxygenated sesquiterpene fraction. Large amounts of α-pinene (4.70%) were found in the hydrocarbonated fractions. To study its possible use as a natural herbicide, the oil was tested in vitro against Amaranthus hybridus, Portulaca oleracea, Chenopodium album, Conyza canadensis and Parietaria judaica, completely inhibiting A. hybridus germination, and nearly blocking C. canadensis and P. judaica germination at all concentrations assayed. In P. oleracea, the oil showed less effect, inhibiting its germination at the higher doses studied. It did not control C. album germination. Regarding seedling length, the oil had strong phytotoxic activity, being effective at all concentrations tested.

Herbicidal activity of Peumus boldus and Drimys winterii essential oils from Chile.

The essential oil composition of Peumus boldus and Drimys winterii was analyzed by means of capillary GC-FID and GC-MS. More than 96% of the total oil components (43 and 54 compounds, respectively) were identified, with ascaridole (51.17 ± 9.51), p-cymene (16.31 ± 2.52) and 1,8-cineole (14.45 ± 2.99) as the main compounds in P. boldus and g-eudesmol (21.65 ± 0.41), followed of elemol (12.03 ± 0.34) and terpinen-4-ol (11.56 ± 1.06) in D. winterii. The herbicidal activity was tested against Amaranthus hybridus and Portulaca oleracea. P. boldus essential oil was the most phytotoxic against both weeds, inhibiting seed germination and seedling growth at all concentrations assayed (0.125-1 µL/mL). D. winterii essential oil did not show any effect on A. hybridus germination and only affected P. oleracea germination at the highest concentration. The results suggest the possible use of the essential oil from P. boldus as a natural herbicide.