Behind the plant-bacteria system: The role of zucchini and its secondary metabolite in shaping functional microbial diversity in MCPA-contaminated soil.

MCPA (2-methyl-4-chlorophenoxyacetic acid) contamination is an emerging problem, especially in water reservoirs. The early removal of MCPA residues from soil can prevent its spread to untreated areas. It has been found that the growth of cucurbits and the addition of selected plant secondary metabolites (PSMs) can stimulate MCPA removal from soil. However, the effect of these treatments on soil microbial activity remains poorly studied. Hence, the aim of this research was to evaluate the influence of zucchini (C. pepo cv Atena Polka) and its characteristic PSM: syringic acid (SA) on the functional diversity of soil microorganisms in MCPA-contaminated soil using Biolog® EcoPlates™. It also examines soil physicochemical properties and the growth parameters of zucchini. Microbial activity was enhanced by both zucchini cultivation and SA. All unplanted variants showed significantly lower microbial activity (average well color development, AWCD, ranging from 0.35 to 0.51) than the planted ones (AWCD ranging from 0.77 to 1.16). SA also stimulated microbial activity in the soil: a positive effect was observed from the beginning of the experiment in the unplanted variants, but over a longer time span in the planted variants. SA ameliorated the toxic effect of MCPA on the studied plants, especially in terms of photosynthetic pigment production: the MCPA+SA group demonstrated significantly increased chlorophyll content (401 ± 4.83 µg/g), compared to the MCPA group without SA (338 ± 50.1 µg/g). Our findings demonstrated that zucchini and the amendment of soils with SA, the characteristic PSM of cucurbits, can shape functional diversity in MCPA-contaminated soil. The changes of soil properties caused by the application of both compounds can trigger changes in functional diversity. Hence, both SA and MCPA exert indirect and direct effects on soil microbial activity.

Novel esterquat-based herbicidal ionic liquids incorporating MCPA and MCPP for simultaneous stimulation of maize growth and fighting cornflower.

Modern agricultural practices are often based on the use of mixtures of specific herbicides to achieve efficient crop protection. The major drawbacks of commercial herbicidal formulations include the necessity to incorporate toxic surfactants and high volatility of active substances. Transformation of herbicides into herbicidal ionic liquids (HILs) seems to be a promising alternative which allows to almost completely reduce volatility due to ionic interactions. In the scope of this research, we transformed (2-methyl-4-chlorophenoxy)acetic acid (MCPA) into a quaternary ester (esterquat) with the use of derivatives of 2-dimethylaminoethanol. The obtained esterquats were later coupled with (±)-2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) in the form of an anion. The combination of MCPA and MCPA is commonly applied in the UK, EU countries and also in the USA to increase the spectrum of targeted weed species. In the framework of this study, novel HILs with an esterquat moiety incorporating a long alkyl chain (C8, C9, C10, C11, C12, C14) were prepared and characterized in terms of basic physicochemical properties (solubility and volatility) as well as biodegradability. Their phytotoxicity was assessed towards cornflower (Centaurea cyanus) as a model weed and maize (Zea mays) as a crop plant. The presence of the esterquat cation contributed to satisfactory solubility in water and other low polar solvents, which eliminates the need to add exogenous adjuvants. Further experiments indicated that the tested HILs stimulated the germination stage of maize and maintained high herbicidal activity towards cornflower. No significant differences in terms of properties were observed in case of HILs which included alkyl substituents with an odd number of carbon atoms. Future studies should be focused on structural modifications in order to improve the biodegradability as well as field studies for evaluation of commercial applications.

Occurrence and transformation of phenoxy acids in aquatic environment and photochemical methods of their removal: a review.

The article presents the behavior of phenoxy acids in water, the levels in aquatic ecosystems, and their transformations in the water environment. Phenoxy acids are highly soluble in water and weakly absorbed in soil. These highly mobile compounds are readily transported to surface and groundwater. Monitoring studies conducted in Europe and in other parts of the world indicate that the predominant phenoxy acids in the aquatic environment are mecoprop, 4-chloro-2-methylphenoxyacetic acid (MCPA), dichlorprop, 2,4-dichlorophenoxyacetic acid (2,4-D), and their metabolites which are chlorophenol derivatives. In water, the concentrations of phenoxy acids are effectively lowered by hydrolysis, biodegradation, and photodegradation, and a key role is played by microbial decomposition. This process is determined by the qualitative and quantitative composition of microorganisms, oxygen levels in water, and the properties and concentrations of phenoxy acids. In shallow and highly insolated waters, phenoxy acids can be decomposed mainly by photodegradation whose efficiency is determined by the form of the degraded compound. Numerous studies are underway on the use of advanced oxidation processes (AOPs) to remove phenoxy acids. The efficiency of phenoxy acid degradation using AOPs varies depending on the choice of oxidizing system and the conditions optimizing the oxidation process. Most often, methods combining UV radiation with other reagents are used to oxidize phenoxy acids. It has been found that this solution is more effective compared with the oxidation process carried out using only UV.

Dissipation of mecoprop-P, isoproturon, bentazon and S-metolachlor in heavy metal contaminated acidic and calcareous soil before and after EDTA-based remediation.

The ability of contaminated farmland soils reclaimed by remediation to dissipate pesticides and thus to mitigate their unwanted environmental effects, i.e., leaching and run-off, was studied. Novel EDTA-based soil washing technology (EDTA and process waters recycling; no toxic emissions) removed 79 and 73% of Pb from acidic and calcareous soil with 740 and 2179 mg kg-1 Pb, respectively. The dissipation kinetics of four herbicides: mecoprop-P, isoproturon, bentazon and S-metolachlor was investigated under field conditions in beds with maize (Zea mays) and barley (Hordeum vulgare). The biphasic First-Order Multi-Compartment (FOMC) model was used to fit experimental data and calculate the herbicides' half-life (DT50) in soil. Remediation significantly (up to 64%) decreased dehydrogenase activity assessed as a marker of soil microbial activity and prolonged the DT50 of herbicides in acidic soils from 16% (isoproturon) to 111% (S-metachlor). Remediation had a less significant effect on herbicide dissipation in calcareous soils; i.e., mecoprop-P DT50 increased by 3%, while isoproturon and S-metachlor DT50 decreased by 29%. Overall, the dissipation from remediated soils was faster than the average DT50 of tested herbicides published in the Pesticides Properties DataBase. Results demonstrate that EDTA-based remediation of the studied soils does not pose any threat of extended herbicide persistence.

Hybrid electrochemical and biological treatment of herbicidal ionic liquids comprising the MCPA anion.

The present study was focused on the application of an electrochemical oxidation process combined with biodegradation for the removal of novel Herbicidal Ionic Liquids (HILs) -promising protection plant products which incorporate herbicidal anions and ammonium cations. The influence of carbon chain length (n = 8, 10, 12, 14, 16, 18) in the dialkyldimethylammonium cations on electrochemical oxidation kinetics, degradation efficiency and biodegradation by activated sludge was investigated. It was established that the applied cation influenced the heterogeneous rate constant and diffusion coefficient of electrochemical oxidation. The oxidation efficiency ranged from 17% in case of HILs with C8 alkyl chain to approx. 60% in case of HILs comprising C14 and C16 alkyl chains after 3 h of electrochemical treatment. Subsequent biodegradation studies revealed that electrochemical oxidation improved the mineralization efficiency of the studied HILs. The mineralization efficiency of electrochemically-treated HILs ranged from 28% in case of HILs comprising the C8 alkyl chain to 57% in case of HILs with C14 and C16 alkyl chains after 28 days. In case of untreated HILs, the corresponding mineralization efficiency ranged from 0 to 8%, respectively. This confirms the feasibility of a hybrid electrochemical-biological approach for treatment of herbicidal ionic liquids based on MCPA.

Photodegradation using TiO2-activated borosilicate tubes.

This study examines the photocatalytic activity of titanium dioxide (TiO2) semiconductor supported on borosilicate tubes (cut-off 290 nm) towards removal of a mix of persistent organic pollutants (POPs) from water. For this purpose, two widely used analgesic and anti-inflammatory drugs (NSAIDs), ibuprofen (IBU) and mefenamic acid, along with MCPA sodium monohydrate, which is a common herbicide frequently used in the agricultural activities, were selected as a case study. Borosilicate tubes were coated with titanium oxide through two different approaches: sol-gel dip-coating and a hybrid nanoparticle dip-coating and plasma-enhanced chemical vapour deposition (PECVD) process. The photochemical reactor that hosts the titania-coated tubes was designed to permit continuous throughput of liquid feed stream. The photodegradation experiments were performed in laboratory conditions under artificial irradiation simulating solar light. The efficiency of direct photolysis and heterogeneous photocatalysis (TiO2) was investigated, and the performance of each coating method was evaluated. Kinetic studies for each experiment were accomplished, the overall results showed poor efficiency and insufficient removal for NSAIDs through direct photolysis, whereas applying heterogeneous photacatalysis with TiO2 coated on borosilicate tubes was found to accelerate their degradation rate with complete decomposition. Concomitantly, kinetic experimental results showed a critical difference of performance for the two coating methods used; in particular, the degradation rates of pollutants by the sol-gel-coated tubes were much faster than the degradation by the nanoparticle/PECVD-coated tubes. Using TiO2 supported on borosilicate tubes appears to be a promising alternative to conventional TiO2 suspension and avoid post-separation stages. The results achieved in this study can be used to optimise large-scale applications, and expanding the study to cover a wide range of pollutants will lead to achieve more representative results.

Preparation and Characterization of Herbicide Mecoprop Imprinted Polymer and Its Application as a Selective Sorbent in Water Sample.

Bulk polymerization method was used to prepare a homogeneous molecularly imprinted polymer (MIP) for the specific extraction of herbicide mecoprop (MCPP). Thereafter, the binding performance of this functional polymer was evaluated under optimal condition, compared to a non-imprinted polymer. From the Scatchard plot analysis, two types of binding sites were detected in the MIP, the high affinity binding sites with a KD (equilibrium dissociation constant) of 6.4 µM and the low affinity ones with a KD of 55.9 µM. In addition, the possibility of using synthesized MIP for MCPP extraction from environmental aqueous samples was explored. The adsorption capacity of MIP in spiked bottled water and groundwater samples showed that the polymer could effectively extract MCPP from bottled water and groundwater (p < 0.05) with the recovery of 70.5% and 65.1%, respectively, demonstrating the potential of imprinted polymers for cost-effective and effective water treatment.

Biodegradable PBAT/PLA Blend with Bioactive MCPA-PHBV Conjugate Suppresses Weed Growth.

The herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) conjugated with poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was prepared via a melt transesterification route. The resultant bioactive oligomer was then mixed with a blend of polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) with different loadings to manufacture films to be used as a bioactive, biodegradable mulch to deliver the herbicide to target broadleaf weed species. The biological targeting of the MCPA-PHBV conjugate in the mulch film was investigated under glasshouse conditions using faba bean (Vicia faba) as a selective (nontarget) model crop species having broadleaf morphology. The presence of the MCPA-PHBV conjugate in the biodegradable PBTA/PLA blend was shown to completely suppress the growth of broadleaf weed species while displaying only a mild effect on the growth of the model crop. The degradation of the mulch film under glasshouse conditions was quite slow. The release of the MCPA-PHBV during this process was detected using NMR, GPC, EDS, and DSC analyses, indicating that the majority of the MCPA diffused out after MCPA-PHBV conjugate bond scission. These data provide a strong "proof of concept" and show that this biodegradable, bioactive film is a good candidate for future field applications and may be of wide agricultural applicability.

Sorption and desorption of glyphosate, MCPA and tetracycline and their mixtures in soil as influenced by phosphate.

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg-1) and elevated (81 to 99 mg kg-1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes.

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH-, BBr3, RuO4, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.

Synthetic polymers blend used in the production of high activated carbon for pesticides removals from liquid phase.

For the activated carbon (AC) production, we used the most common industrial and consumer solid waste, namely polyethyleneterephthalate (PET), alone or blended with other synthetic polymer such polyacrylonitrile (PAN). By mixing PET, with PAN, an improvement in the yield of the AC production was found and the basic character and some textural and chemical properties were enhanced. The PET-PAN mixture was subjected to carbonisation, with a pyrolysis yield of 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The AC revealed a high surface area (1400, 1230 and 1117 m2 g-1) and pore volume (0.46, 0.56 and 0.50 cm3 g-1), respectively, for PET, PAN and PET-PAN precursors. Selected ACs were successfully tested for 4-chloro-2-methylphenoxyacetic acid (MCPA) and diuron removal from the liquid phase, showing a higher adsorption capacity (1.7 and 1.2 mmol g-1, respectively, for MCPA and diuron) and good fits with the Langmuir (PET) and Freundlich equation (PAN and PET-PAN blend). With MCPA, the controlling factor to the adsorption capacity was the porous volume and the average pore size. Concerning diuron, the adsorption was controlled essentially by the external diffusion. A remarkable result is the use of different synthetic polymers wastes, as precursors for the production of carbon materials, with high potential application on the pesticides removals from the liquid phase.

Alkyl(C16, C18, C22)trimethylammonium-Based Herbicidal Ionic Liquids.

In the framework of this study a synthesis methodology and characterization of long alkyl herbicidal ionic liquids (HILs) based on four commonly used herbicides (2,4-D, MCPA, MCPP, and dicamba) are presented. New HILs were obtained with high efficiency (>95%) using an acid-base reaction between herbicidal acids and hexadecyltrimethylammonium, octadecyltrimethylammonium, and behenyltrimethylammonium hydroxides in alcoholic medium. Among all synthesized salts, only three compounds comprising the MCPP anion were liquids at room temperature. Subsequently, the influence of both the alkyl chain length and the anion structure on their physicochemical properties (thermal decomposition profiles, solubility in 10 representative solvents, surface activity, density, viscosity, and refractive index) was determined. All HILs exhibited high thermal stability as well as surface activity; however, their solubility notably depended on both the length of the carbon chain and the structure of the anion. The herbicidal efficacy of the obtained salts was tested in greenhouse and field experiments. Greenhouse testing performed on common lambsquarters (Chenopodium album L.) and flixweed (Descurainia sophia L.) as test plants indicated that HILs were characterized by similar or higher efficacy compared to commercial herbicides. The results of field trials confirmed the high activity of HILs, particularly those containing phenoxyacids as anions (MCPA, 2,4-D, and MCPP).

Influence of 2,4-D and MCPA herbicides on uptake and translocation of heavy metals in wheat (Triticum aestivum L.).

The aim of the study was to estimate the influence of the 2,4-dichlorophenoxy acetic acid and 2-methyl-4-chlorophenoxyacetic acid on the uptake and translocation of Cd, Co, Ni, Cu, Zn, Pb and Mn by wheat (Triticum aestivum L.). Two farmland soils typical for the central Polish rural environment were used. Studies involved soil analyses, contents of bioavailable, exchangeable and total forms for all investigated metals. Atomic absorption spectrometry was used to determine the concentration of the elements. The best correlation between the herbicide rate and the metal concentration was visibly for the underground part of plants. Analysis of variance proved that herbicide treatment of wheat frequently influences the metal transfer from soil and their concentration in roots and shoots. In particular, higher herbicide rates prompted the significant increase of all metals concentration in roots. Additionally, transfer coefficients depended on the type of soil and the herbicide rate applied. Uptake of metals may be also influenced by the formation of sparingly water-soluble metal-herbicide complexes. Its intensity would then depend on the solubility of particular chemical entity with the low solvable Pb, Cu and Cd complexes being the least mobile.

Photocatalytic ozonation of pesticides in a fixed bed flow through UVA-LED photoreactor.

In this study, a fixed bed flow through UVA-LED photoreactor was used to compare the efficiency of ozone, photocatalysis and photocatalysis-ozone degradation, and mineralization of two pure pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and a commercial one, Killex®. For the degradation of the parent compounds, ozone-based processes were more effective. While for mineralization, photocatalytic processes were more effective. Photocatalytic ozonation was the most efficient process for both the degradation and mineralization of the parent compounds. The degradation rates and mineralization by photocatalytic ozonation were higher than the summation of the corresponding rates by ozonation and photocatalysis, indicating a symbiotic relationship.Overall, the photocatalytic ozonation process with the fixed bed TiO2 reduces the time needed for the degradation and mineralization of the pesticides, reduces the costs of powder catalyst separation and overcomes the reduced efficiency of immobilized catalysts, which makes the process quite attractive for practical applications.

Influence of oligomeric herbicidal ionic liquids with MCPA and Dicamba anions on the community structure of autochthonic bacteria present in agricultural soil.

The aim of this study was to evaluate the impact of selected herbicidal ionic liquids (HILs), which exhibit high efficacy in terms of weed control and low toxicity, but may be persistent due to limited biodegradability, on the community structure of autochthonic bacteria present in agricultural soil. Four different oligomeric HILs (with two types of cations and different ratio of herbicidal anions) were synthesized and characterized by employing (1)H and (13)C NMR. The results of biodegradation assay indicated that none of the tested HILs could be classified as readily biodegradable (biodegradation rate ranged from 0 to 7%). The conducted field studies confirmed that the herbicidal efficacy of the HILs was higher compared to the reference herbicide mixture by 10 to 30%, depending on the dose and weed species. After termination of field studies, the soil treated with the tested HILs was subjected to next generation sequencing in order to investigate the potential changes in the bacterial community structure. Proteobacteria was the dominant phylum in all studied samples. Treatment with the studied HILs resulted in an increase of Actinobacteria compared to the reference herbicidal mixture. Differenced among the studied HILs were generally associated with a significantly higher abundance of Bacteroidetes in case of 1-HIL-Dicamba 1/3 and Firmicutes in case of 2-HIL-Dicamba 1/3.

Selective and Sensitive Chemiluminescence Determination of MCPB: Flow Injection and Liquid Chromatography.

Two new chemiluminescence (CL) methods are described for the determination of the herbicide 4-(4-chloro-o-tolyloxy) butyric acid (MCPB). First, a flow injection chemiluminescence (FI-CL) method is proposed. In this method, MCPB is photodegraded with an ultraviolet (UV) lamp and the photoproducts formed provide a great CL signal when they react with ferricyanide in basic medium. Second, a high-performance liquid chromatography chemiluminescence (HPLC-CL) method is proposed. In this method, before the photodegradation and CL reaction, the MCPB and other phenoxyacid herbicides are separated in a C18 column. The experimental conditions for the FI-CL and HPLC-CL methods are optimized. Both methods present good sensitivity, the detection limits being 0.12 µg L(-1) and 0.1 µg L(-1) (for FI-CL and HPLC-CL, respectively) when solid phase extraction (SPE) is applied. Intra- and interday relative standard deviations are below 9.9%. The methods have been satisfactorily applied to the analysis of natural water samples. FI-CL method can be employed for the determination of MCPB in simple water samples and for the screening of complex water samples in a fast, economic, and simple way. The HPLC-CL method is more selective, and allows samples that have not been resolved with the FI-CL method to be solved.

Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop - Kinetics and reaction product formation.

The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800 mJ/cm(2) and 5 mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000 mJ/cm(2) and 15 mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6 × 10(8), 2.0 × 10(8) and 1.1 × 10(9) M(-1) s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed.

Adsorption and characterization of MCPA on DDTMA- and raw-montmorillonite: Surface sites involved.

The 4-chloro-2-methylphenoxy acid (MCPA) is an herbicide widely used in agriculture, which generates a great concern about contamination of surface water and serious consequences for human health and the environment. In this work, the adsorption of MCPA on an Argentine montmorillonite (MMT) and its organo-montmorillonite product (OMMT) with different dodecyl trimethyl ammonium loading was investigated. MCPA adsorption on OMMT increases at least 3 times, with respect to the amount determined for MMT. X-ray diffraction and zeta potential analyses indicated the inner (interlayer) and outer surface participate as adsorption sites. Changes in surface electric charge and also interlayer expansion suggest that dimethyl amine (MCPA counterion) was also surface-adsorbed. The larger aggregates of OMMT, without and with MCPA, obtained compared to those of MMT samples, generate an improvement in the coagulation efficiency. This property, particularly after MCPA retention, allows an easier separation of the solids from the solution and enables a simple technological process application.

Imprinting of molecular recognition sites combined with π-donor-acceptor interactions using bis-aniline-crosslinked Au-CdSe/ZnS nanoparticles array on electrodes: Development of electrochemiluminescence sensor for the ultrasensitive and selective detection of 2-methyl-4-chlorophenoxyacetic acid.

A novel strategy is reported for the fabrication of bis-aniline-crosslinked Au nanoparticles (NPs)-CdSe/ZnS quantum dots (QDs) array composite by facil one-step co-electropolymerization of thioaniline-functionalized AuNPs and thioaniline-functionalized CdSe/ZnS QDs onto thioaniline-functionalized Au elctrodes (AuE). Stable and enhanced cathodic electrochemiluminescence (ECL) of CdSe/ZnS QDs is observed on the modified electrode in neutral solution, suggesting promising applications in ECL sensing. An advanced ECL sensor is explored for detection of 2-methyl-4-chlorophenoxyacetic acid (MCPA) which quenches the ECL signal through electron-transfer pathway. The sensitive determination of MCPA with limit of detection (LOD) of 2.2 nmolL(-1) (S/N=3) is achieved by π-donor-acceptor interactions between MCPA and the bis-aniline bridging units. Impressively, the imprinting of molecular recognition sites into the bis-aniline-crosslinked AuNPs-CdSe/ZnS QDs array yields a functionalized electrode with an extremely sensitive response to MCPA in a linear range of 10 pmolL(-1)-50 µmolL(-1) with a LOD of 4.3 pmolL(-1 ()S/N=3). The proposed ECL sensor with high sensitivity, good selectivity, reproducibility and stability has been successfully applied for the determination of MCPA in real samples with satisfactory recoveries. In this study, ECL sensor combined the merits of QDs-ECL and molecularly imprinting technology is reported for the first time. The developed ECL sensor holds great promise for the fabrication of QDs-based ECL sensors with improved sensitivity and furthermore opens the door to wide applications of QDs-based ECL in food safety and environmental monitoring.

Comparative study on the biodegradability of morpholinium herbicidal ionic liquids.

This study focused on evaluating the toxicity as well as primary and ultimate biodegradability of morpholinium herbicidal ionic liquids (HILs), which incorporated MCPA, MCPP, 2,4-D or Dicamba anions. The studied HILs were also subjected to determination of surface active properties in order to assess their influence on toxicity and biodegradability. The study was carried out with microbiota isolated from different environmental niches: sediments from river channel, garden soil, drainage trench collecting agricultural runoff stream, agricultural soil and municipal waste repository. The obtained results revealed that resistance to toxicity and biodegradation efficiency of the microbiota increased in the following order: microbiota from the waste repository > microbiota from agricultural soil ≈ microbiota from an agricultural runoff stream > microbiota from garden soil > microbiota from the river sludge. It was observed that the toxicity of HILs increased with the hydrophobicity of the cation, however the influence of the anion was more notable. The highest toxicity was observed when MCPA was used as the anion (EC50 values ranging from 60 to 190 mg L(-1)). The results of ultimate biodegradation tests indicated that only HILs with 2,4-D as the anion were mineralized to some extent, with slightly higher values for HILs with the 4-decyl-4-ethylmorpholinium cation (10-31 %) compared to HILs with the 4,4-didecylmorpholinium cation (9-20 %). Overall, the cations were more susceptible (41-94 %) to primary biodegradation compared to anions (0-61 %). The obtained results suggested that the surface active properties of the studied HILs may influence their toxicity and biodegradability by bacteria in different environmental niches.