Ecotoxicity of the Adipate Plasticizers: Influence of the Structure of the Alcohol Substituent.

A significant increase in the production of plastic materials and the expansion of their areas of application contributed to the accumulation of a large amount of waste of polymeric materials. Most of the polymer composition is made up of plasticizers. Phthalate plasticizers have been recognized as potentially hazardous to humans and the environment due to the long period of their biodegradation and the formation of persistent toxic metabolites. It is known that the industrial plasticizer dioctyl adipate is characterized by reduced toxicity and a short biodegradation period. The paper describes the synthesis of a number of new asymmetric esters based on adipic acid and ethoxylated butanol by azeotropic esterification. The receipt of the products was confirmed by IR spectra. The physicochemical properties of the synthesized compounds were investigated. The glass transition temperatures of PVC composites plasticized with alkyl butoxyethyl adipates were determined using DSC analysis. The ecological safety of esters was assessed by the phytotesting method. Samples of adipates were tested for fungal resistance, and the process of their biodegradation in soil was also studied. It is shown that the synthesized esters have good plasticizing properties and are environmentally safe. When utilized under natural conditions, they can serve as a potential source of carbon for soil microorganisms and do not form stable toxic metabolites; therefore, they are not able to accumulate in nature; when the plasticizers under study are disposed of in the soil, toxic substances do not enter.

Discovery of novel potential plant growth regulators from Corydalis mucronifera.

Three pairs of enantiomers mucroniferals A-C (1-3), with a novel skeleton of 1,4-epoxynaphthalene-2,3-dicarboxylic acid first reported from nature source, were isolated from Corydalis mucronifera. Their structures were elucidated based on extensive spectroscopic data analysis of MS, 1D and 2D NMR, and their absolute configurations were confirmed by single-crystal X-ray diffraction analysis and comparison of the experimental and calculated ECD data. Mucroniferals A-C showed broad-spectrum inhibitory activities on seedling growth of all plants tested (Lepidium apetalum, Raphanus sativus, Lactuca sativa, and Arabidopsis thaliana) with a dose-dependent relationship. Additionally, mucroniferals A and B exhibited significant inhibitory effects on germination of most seeds at concentration of 80 µg/mL, and the inhibition was reversible.

Ecotoxicity Evaluation of Pristine and Indolicidin-coated Silver Nanoparticles in Aquatic and Terrestrial Ecosystem.

BACKGROUND: Metallic nanoparticles (NPs) are highly exploited in manufacturing and medical processes in a broad spectrum of industrial applications and in the academic sectors. Several studies have suggested that many metallic nanomaterials including those derived by silver (Ag) are entering the ecosystem to cause significant toxic consequences in cell culture and animal models. However, ecotoxicity studies are still receiving limited attention when designing functionalized and non.-functionalized AgNPs. OBJECTIVE: This study aimed to investigate different ecotoxicological profiles of AgNPs, which were analyzed in two different states: in pristine form uncoated AgNPs and coated AgNPs with the antimicrobial peptide indolicidin. These two types of AgNPs are exploited for a set of different tests using Daphnia magna and Raphidocelis subcapitata, which are representatives of two different levels of the aquatic trophic chain, and seeds of Lepidium sativum, Cucumis sativus and Lactuca sativa. RESULTS: Ecotoxicological studies showed that the most sensitive organism to AgNPs was crustacean D. magna, followed by R. subcapitata and plant seeds, while AgNPs coated with indolicidin (IndAgNPs) showed a dose-dependent decreased toxicity for all three. CONCLUSION: The obtained results demonstrate that high ecotoxicity induced by AgNPs is strongly dependent on the surface chemistry, thus the presence of the antimicrobial peptide. This finding opens new avenues to design and fabricate the next generation of metallic nanoparticles to ensure the biosafety and risk of using engineered nanoparticles in consumer products.

Comparative proteomics analysis of whitetop (Lepidium draba L.) seedlings in response to exogenous glucose.

In this research, a comparative proteomics approach was conducted to understand the physiological processes behind the sulforaphane formation in whitetop seedlings in response to exogenous glucose. Initially, 5-day-old whitetop seedlings were elicited by different concentrations (0, 166, 250, 277, 360 mM) of glucose for 72 h. According to the results, sulforaphane formation was influenced in a dose-dependent manner by glucose, and was maximized with the concentrations of 166 and 250 mM. Consequently, 2-dimensional gel electrophoresis was performed on the 166 mM glucose-elicited seedlings and it was shown that 25 protein spots were differentially expressed between glucose-elicited seedlings and control. Two hypothetical (were down-regulated) and 9 unique proteins (44% and 56% up- and down-regulated, respectively) were identified based on the Mass spectrometry analysis. According to the functional classification of the unique proteins, photosynthetic, chaperone, energy metabolism, signaling and sorting related proteins are marked in response to the glucose elicitation. This is the first report to successfully identify the Abscisic acid receptor PYR1-like and sorting nexin 1 isoform X1 by proteomics technique. In addition, the role of the sorting nexin 1 isoform X1 in the glucose-elicited whitetop seedling is reported for the first time.

Metronidazole removal by means of a combined system coupling an electro-Fenton process and a conventional biological treatment: By-products monitoring and performance enhancement.

In order to mineralize Metronidazole (MTZ), a process coupling an electro-Fenton pretreatment and a biological degradation was implemented. A mono-compartment batch reactor containing a carbon-felt cathode and a platinum anode was employed to carry out the electro-Fenton pretreatment of MTZ. A total degradation of MTZ (100 mg L-1) was observed at 0.07 mA.cm-2 after only 20 min of electrolysis. Yet, after 1 and 2 h of electrolysis, the mineralization level remained low (16.2% and 32% respectively), guaranteeing a significant residual organic content for further biological treatment. LCMS/MS was used to determine the intermediates by-products and hence to propose a plausible degradation pathway. An increase from 0 to 0.44 and 0.6 for 1 and 2 h of electrolysis was observed for the BOD5/COD ratio. Thus, from 1 h of electro-Fenton pretreatment, the electrolysis by-products were considered biodegradable. A biological treatment of the electrolysis by-products after 1 and 2 h was then realized. The mineralization yields reached very close values, about 84% for 1 and 2 h of electrolysis after 504 h of biological treatment, namely close to 89% for the overall process, showing the pertinence of the proposed coupled process.

Assessing the potential phytotoxicity of digestate from winery wastes.

In this study, digestate from winery wastes was investigated focusing on phytotoxicity using macrophytes and evaluating the potential contribution of ammonium and copper. Spreading of digestate on soil could represent a suitable approach to recycle nutrients and organic matter, creating an on site circular economy. In this study, digestate quality was evaluated considering both chemical-physical characteristics and biological toxicity applying germination test. The effluent did not meet the entire amendment quality standard defined by Italian law (Decree 75/2010 germination index > 60% with solution of 30% v/v of digestate), but bio-stimulation was observed at low doses (3.15-6.25% v/v) for S. alba and S. saccharatum. The beneficial concentration agreed with Nitrate Directive dose and suggested that limited addition of digestate could have several positive effects on soil characteristics and on crop growth. Specific test using ammonium and copper solutions showed that these pollutants were not directly correlated to observed phytotoxicity.

Application of biochar to sewage sludge reduces toxicity and improve organisms growth in sewage sludge-amended soil in long term field experiment.

The aim of the present study was to determine changes in the physicochemical properties and toxicity of soil amended with sewage sludge (10tdw/ha) or sewage sludge (10tdw/ha) with biochar addition (2.5, 5 or 10% of sewage sludge). The study was carried out as a field experiment over a period of 18months. Samples for analysis were taken at the beginning of the experiment as well as after 6, 12 and 18months. The study investigated toxicity of the unamended soil, sewage sludge-amended soil and sewage sludge-amended soil with biochar addition towards Folsomia candida (collembolan test) and Lepidium sativum (Phytotoxkit F). Moreover, toxicity of aqueous extracts obtained from the tested soils towards Vibrio fischeri (Microtox®) and Lepidium sativum (elongation test) was determined. The study showed that addition of biochar to the sewage sludge and soil reduced leaching of nutrients (mainly phosphorus and potassium) from the amended soil. Biochar significantly reduced sewage sludge toxicity, exhibiting a stimulating effect on the tested organisms. The stimulating effect of biochar addition to the sewage sludge persisted throughout the entire experiment. Apart from the remediatory character of biochar, this is also evidence of its fertilizing character. In the tests with L. sativum (leachates and solid phase) and V. fischeri (leachates), increasing the rate of biochar in the sewage sludge increased root growth stimulation (L. sativum) and bacteria luminescence (V. fischeri). However, increasing biochar rate decreased F. candida reproduction stimulation, which could have been an effect of reduced nutrient bioavailability due to the biochar.

Comparative genome analysis of the vineyard weed endophyte Pseudomonas viridiflava CDRTc14 showing selective herbicidal activity.

Microbes produce a variety of secondary metabolites to be explored for herbicidal activities. We investigated an endophyte Pseudomonas viridiflava CDRTc14, which impacted growth of its host Lepidium draba L., to better understand the possible genetic determinants for herbicidal and host-interaction traits. Inoculation tests with a variety of target plants revealed that CDRTc14 shows plant-specific effects ranging from beneficial to negative. Its herbicidal effect appeared to be dose-dependent and resembled phenotypically the germination arrest factor of Pseudomonas fluorescens WH6. CDRTc14 shares 183 genes with the herbicidal strain WH6 but the formylaminooxyvinylglycine (FVG) biosynthetic genes responsible for germination arrest of WH6 was not detected. CDRTc14 showed phosphate solubilizing ability, indole acetic acid and siderophores production in vitro and harbors genes for these functions. Moreover, genes for quorum sensing, hydrogen cyanide and ACC deaminase production were also found in this strain. Although, CDRTc14 is related to plant pathogens, we neither found a complete pathogenicity island in the genome, nor pathogenicity symptoms on susceptible plant species upon CDRTc14 inoculation. Comparison with other related genomes showed several unique genes involved in abiotic stress tolerance in CDRTc14 like genes responsible for heavy metal and herbicide resistance indicating recent adaptation to plant protection measures applied in vineyards.

Phytotoxicity of cardoon (Cynara cardunculus) allelochemicals on standard target species and weeds.

Cardoon (Cynara cardunculus L.) is a native plant to the Iberian Peninsula and the European Atlantic coast and invasive in American environments. Different solvents were used to perform cardoon extracts that were tested in phytotoxic bioassays. The ethyl acetate extract had the highest inhibitory activity so this was tested on the germination and growth of standard target species (lettuce, watercress, tomato, and onion) and weeds (barnyardgrass and brachiaria). The ethyl acetate extract was very active on root growth in both standard target species and weeds and it was therefore fractionated by chromatography. The spectroscopic data showed that the major compounds were sesquiterpene lactones. Aguerin B, grosheimin, and cynaropicrin were very active on etiolated wheat coleoptile, standard target species, and weed growth. The presence of these compounds explains the bioactivity of the ethyl acetate extract. The strong phytotoxicity of these compounds on important weeds shows the potential of these compounds as natural herbicide models.

Stomatal and pavement cell density linked to leaf internal CO2 concentration.

BACKGROUND AND AIMS: Stomatal density (SD) generally decreases with rising atmospheric CO2 concentration, Ca. However, SD is also affected by light, air humidity and drought, all under systemic signalling from older leaves. This makes our understanding of how Ca controls SD incomplete. This study tested the hypotheses that SD is affected by the internal CO2 concentration of the leaf, Ci, rather than Ca, and that cotyledons, as the first plant assimilation organs, lack the systemic signal. METHODS: Sunflower (Helianthus annuus), beech (Fagus sylvatica), arabidopsis (Arabidopsis thaliana) and garden cress (Lepidium sativum) were grown under contrasting environmental conditions that affected Ci while Ca was kept constant. The SD, pavement cell density (PCD) and stomatal index (SI) responses to Ci in cotyledons and the first leaves of garden cress were compared. (13)C abundance (δ(13)C) in leaf dry matter was used to estimate the effective Ci during leaf development. The SD was estimated from leaf imprints. KEY RESULTS: SD correlated negatively with Ci in leaves of all four species and under three different treatments (irradiance, abscisic acid and osmotic stress). PCD in arabidopsis and garden cress responded similarly, so that SI was largely unaffected. However, SD and PCD of cotyledons were insensitive to Ci, indicating an essential role for systemic signalling. CONCLUSIONS: It is proposed that Ci or a Ci-linked factor plays an important role in modulating SD and PCD during epidermis development and leaf expansion. The absence of a Ci-SD relationship in the cotyledons of garden cress indicates the key role of lower-insertion CO2 assimilation organs in signal perception and its long-distance transport.

[Isotopic effects of low concentration of deuterium in water on biological systems].

Isotopic effects of deuterium in water are studied in a broad range of concentrations on a number of biological objects of different organization levels. The results obtained show that biological objects are sensitive to variations of isotope composition in water. A decrease or increase in deuterium concentrations in water may cause activation or inhibition of biological functions. The values of biological isotopic effects of low deuterium concentration may even be higher than those of high deuterium concentration. No regularity in response for all the objects studied failed to find out in a range of deuterium concentration in water from 4 ppm to 1%.

Chemical composition, antimicrobial, insecticidal, phytotoxic and antioxidant activities of Mediterranean Pinus brutia and Pinus pinea resin essential oils.

Essential oils of the resins of Pinus brutia and Pinus pinea were evaluated for their biological potential. Essential oils were characterized using GC-MS and GC/FID. in vitro antimicrobial, phytotoxic, antioxidant, and insecticidal activities were carried out using the direct contact and the fumigant assays, respectively. The chemical profile of the essential oils of the resins of P. pinea and P. brutia included mainly α-pinene (21.39% and 25.40%), ß-pinene (9.68% and 9.69%), and caryophyllene (9.12% and 4.81%). The essential oils of P. pinea and P. brutia exerted notable antimicrobial activities on Micrococcus luteus and Bacillus subtilis, insecticidal activities on Ephestia kuehniella eggs, phytotoxic activities on Lactuca sativa, Lepidium sativum, and Portulaca oleracea, as well as antioxidant potential. Indications of the biological activities of the essential oils suggest their use in the formulation of ecofriendly and biocompatible pharmaceuticals.

Calcium promotes activity and confers heat stability on plant peroxidases.

In this paper we demonstrate how peroxidase (PO) activities and their heat stability correlate with the availability of free Ca(2+) ions. Calcium ions work as a molecular switch for PO activity and exert a protective function, rendering POs heat stable. The concentration ranges of these two activities differ markedly. POs are activated by µM Ca(2+) concentration ranges, whereas heat stabilization is observed in the nM range. This suggests the existence of different Ca(2+) binding sites. The heat stability of POs depends on the source plant species. Terrestrial plants have POs that exhibit higher temperature stability than those POs from limnic and marine plants. Different POs from a single species can differ in terms of heat stability. The abundance of different POs within a plant is dependent on age and developmental stage. The heat stability of a PO does not necessarily correlate with the maximum temperature the source species is usually exposed to in its natural habitat. This raises questions on the role of POs in the heat tolerance of plants. Consequently, detailed investigations are needed to identify and characterize individual POs, with regard to their genetic origin, subcellular expression, tissue abundance, developmental emergence and their functions in innate and acquired heat tolerance.

A comparison regarding antiproliferative action between soy total extract and genistein.

The aim of this study is to make a comparison between the action of genistein and total soy extract regarding anticancer action on two different in vivo models: phytobiological test and animal model, and to see which of the two tested samples present a greater antiproliferative effect. Soybean seeds were grounded and a solvent formed of DMSO-ethanol-water in rapport 5-70-25 v/v/v was prepared. The extraction was made using an ultrasonic bath (Falc LCD Series) for 30 minutes, 59 kHz. The solvent was evaporated with a rotary evaporator at 50°C. Genistein was acquired from Extrasynthèse (France), hydroxypropyl-γ-cyclodextrin (HPGCD) from Cyclolab Hungary, 7,12-dimethylbenz[a]anthracene (DMBA), dimethylsulfoxide (DMSO), and 12-O-tetradecanoylphorbol-13-acetate (TPA) from Sigma Aldrich, Germany. Because of the poor water solubility, genistein was prepared in a complex with hydroxypropyl-γ-cyclodextrin in a molar ratio 1:2 by kneading method and total soy extract in a mass ratio 1:4 also by kneading method. Phytobiological test indicated an inhibition index over 50% in case of solutions of concentration between 8-33% in both samples, suggesting a possible antiproliferative action at a superior level. Study on C57BL/6J mice was made on which it was induced cancer with physical agents like DMBA, and it was promoted with TPA. Mice where divided in four groups: Group A - blank group, Group B - mice who received total soy extract, Group C - mice who received genistein, Group D - untreated mice. Results on animal model show that both soy total extract and genistein inhibited the initiation and promotion of chemically-induced skin tumorigenesis, but genistein had a greater success in recovering skin lesions type experimental malignant melanoma.

Seeds of Brassicaceae weeds have an inherent or inducible response to the germination stimulant karrikinolide.

BACKGROUND AND AIMS: Karrikinolide (KAR(1)) is a smoke-derived chemical that can trigger seeds to germinate. A potential application for KAR(1) is for synchronizing the germination of weed seeds, thereby enhancing the efficiency of weed control efforts. Yet not all species germinate readily with KAR(1), and it is not known whether seemingly non-responsive species can be induced to respond. Here a major agronomic weed family, the Brassicaceae, is used to test the hypothesis that a stimulatory response to KAR(1) may be present in physiologically dormant seeds but may not be expressed under all circumstances. METHODS: Seeds of eight Brassicaceae weed species (Brassica tournefortii, Raphanus raphanistrum, Sisymbrium orientale, S. erysimoides, Rapistrum rugosum, Lepidium africanum, Heliophila pusilla and Carrichtera annua) were tested for their response to 1 µm KAR(1) when freshly collected and following simulated and natural dormancy alleviation, which included wet-dry cycling, dry after-ripening, cold and warm stratification and a 2 year seed burial trial. KEY RESULTS: Seven of the eight Brassicaceae species tested were stimulated to germinate with KAR(1) when the seeds were fresh, and the remaining species became responsive to KAR(1) following wet-dry cycling and dry after-ripening. Light influenced the germination response of seeds to KAR(1), with the majority of species germinating better in darkness. Germination with and without KAR(1) fluctuated seasonally throughout the seed burial trial. CONCLUSIONS: KAR(1) responses are more complex than simply stating whether a species is responsive or non-responsive; light and temperature conditions, dormancy state and seed lot all influence the sensitivity of seeds to KAR(1), and a response to KAR(1) can be induced. Three response types for generalizing KAR(1) responses are proposed, namely inherent, inducible and undetected. Given that responses to KAR(1) were either inherent or inducible in all 15 seed lots included in this study, the Brassicaceae may be an ideal target for future application of KAR(1) in weed management.

Isolation and phytotoxicity of terpenes from Tectona grandis.

A study was carried out on the allelopathic potential of four forest species, Tectona grandis, Aleurites fordii, Gliricidia sepium, and Maytenus buxifolia. The most active species, T. grandis, was selected to perform a phytochemical study. A new compound, abeograndinoic acid, was isolated, and elucidation of its structure showed that this compound has an unusual carbon skeleton. A further 21 known terpenoids-including 4 sesquiterpenoids, 8 diterpenes and 9 triterpenes-also were isolated. A biosynthetic scheme for the presence of the new compound is proposed. Bioactivity profiles that used etiolated wheat coleoptiles and phytotoxicity bioassays on the isolated compounds were conducted. The compounds that presented the highest phytotoxic activity are the diterpenes 9 (2-oxokovalenic acid) and 12 (19-hydroxyferruginol).

Chemical composition and antigerminative activity of the essential oils from five Salvia species.

The chemical composition of the essential oils of Salvia africana L., Salvia elegans Vahl, Salvia greggii A. Gray, Salvia mellifera Green and Salvia munzii Epling, cultivated in Eboli (Salerno, Southern Italy), was studied by means of GC and GC-MS analyses. In all, 88 compounds were identified, 54 for S. africana, accounting for 95.4% of the total oil, 55 for S. elegans (92.9%), 50 for S. greggii (96.9%), 54 for S. mellifera (90.4%) and 47 for S. munzii (97.5%), respectively. In S. africana,the amount of monoterpenoids and sesquiterpenoids is very similar. For other species, the monoterpenoid percentage is greater than the amount of sesquiterpenoids. The oils of S. elegans, S. greggii and S. munzii were active inhibitors of germination and radical elongation of Raphanus sativus L. and Lepidium sativum L.

Chemical composition and phytotoxic effects of essential oils of Salvia hierosolymitana Boiss. and Salvia multicaulis Vahl. var. simplicifolia Boiss. growing wild in Lebanon.

The chemical composition of the essential oils of S. hierosolymitana Boiss. and S. multicaulis Vahl. var. simplicifolia Boiss. collected in Lebanon was studied by means of GC and GC-MS analysis. In all 115 compounds were identified: 82 for S hierosolymitana and 72 for S. multicaulis var. simplicifolia. The presence of carbonylic compounds (17%) characterizes the oil from S. hierosolymitana,while S. multicaulis var. simplicifolia oil is rich of monoterpenes (34.5%) and sesquiterpenes (46.9%). The effects of the essential oils on germination and initial radical elongation of Raphanus sativus L. (radish) and Lepidium sativum L. (garden cress) were studied, indicating in a different activity against radical elongation of the species tested.

Effect of commercial mineral-based additives on composting and compost quality.

The effectiveness of two commercial additives meant to improve the composting process was studied in a laboratory-scale experiment. Improver A (sulphates and oxides of iron, magnesium, manganese, and zinc mixed with clay) and B (mixture of calcium hydroxide, peroxide, and oxide) were added to source-separated biowaste:peat mixture (1:1, v/v) in proportions recommended by the producers. The composting process (T, emissions of CO(2), NH(3), and CH(4)) and the quality of the compost (pH, conductivity, C/N ratio, water-soluble NH(4)-N and NO(3)-N, water- and NaOH-soluble low-weight carboxylic acids, nutrients, heavy metals and phytotoxicity to Lepidium sarivum) were monitored during one year. Compared with the control, the addition of improver B increased pH by two units, led to an earlier elimination of water-soluble ammonia, an increase in nitrates, a 10-fold increase in concentrations of acetic acid, and shortened phytotoxicity period by half; as negative aspect it led to volatilization of ammonia. The addition of improver A led to a longer thermophilic stage by one week and lower concentrations of low-weight carboxylic acids (both water- and NaOH-extractable) with formic and acetic of similar amounts, however, most of the aspects claimed by the improver's producer were not confirmed in this trial.

Tulasnein and podospirone from the coprophilous xylariaceous fungus Podosordaria tulasnei.

Tulasnein (1), a new metabolite with strong antimicrobial and weaker cytotoxic and phytotoxic activity, was isolated from culture filtrates of three strains of the xylariaceous coprophilous fungus Podosordaria tulasnei. The producing strains were identified by their rhizomorphs and by ITS rDNA sequence analysis. A second new metabolite, podospirone (2), was also produced by all three strains whereas the weakly cytotoxic (+)-3,4-anhydroshikimic acid methyl ester (3) was detected in only one strain.