Computational design and preparation of water-compatible noncovalent imprinted microspheres.

Herein, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model template in a rational design strategy to produce water-compatible noncovalent imprinted microspheres. The proposed approach involved computational modelling for screening functional monomers and a simple method for preparing monodisperse and highly cross-linked microspheres. The fabricated non-imprinted polymer (NIP) and 2,4-d-imprinted polymer (2,4-d-MIP) were characterised, and their adsorption capabilities in an aqueous environment were evaluated. Results reveal that the pseudo-second-order kinetics model was appropriate for representing the adsorption of 2,4-D on NIP and 2,4-d-MIP, with R2 values of 0.97 and 0.99, respectively. The amount of 2,4-D adsorbed on 2,4-d-MIP (97.75 mg g-1) was considerably higher than those of phenoxyacetic acid (35.77 mg g-1), chlorogenic acid (9.72 mg g-1), spiramycin (1.56 mg g-1) and tylosin (1.67 mg g-1). Furthermore, it exhibited strong resistance to protein adsorption in an aqueous medium. These findings confirmed the feasibility of the proposed approach, providing a reference for the development of water-compatible noncovalent imprinted polymers.

CdIn2Se4@chitosan heterojunction nanocomposite with ultrahigh photocatalytic activity under sunlight driven photodegradation of organic pollutants.

This research focused on synthesizing a CdIn2Se4@Ch nanocomposite by doping CdIn2Se4 into chitosan using a photolysis assisted ultrasonic process. The aim was to enhance the photodegradation efficiency of ofloxacin and 2,4-dichlorophenoxyacetic acid under sunlight. The synthesized CdIn2Se4@Ch nanocomposite was investigated via different techniques, including XRD, XPS, FTIR, TEM, DSC, TGA, UV-Vis and PL. The study also investigated the influence of various reaction parameters, including the effects of inorganic and organic ions. The synthesized nanocomposite demonstrated exceptional efficiency, achieving 86 % and 95 % removal rates, with corresponding rate constants of 0.025 and 0.047 min-1. This performance surpasses that of CdIn2Se4 by approximately 1.35 and 2.25 times, respectively. The values of COD were decreased to 78 and 86 % for ofloxacin and 2,4-dichlorophenoxyacetic, while the TOC values decreased to 71 and 84 %, respectively, from their premier values. The improvement in performance is associated with the introduction of CdIn2Se4 into chitosan, resulting in the self-integration of Cd into the catalyst. This creates a localized accumulation point for electrons, enhancing the efficiency of charge separation and further reducing the surface charge of chitosan. Experimental evidence suggests that superoxide and hydroxyl radicals play a significant role in the photodegradation of pollutants. Additionally, the nanocomposite exhibits excellent stability and can be reused up to five times, indicating remarkable stability and reusability of the developed photocatalyst.

The potential of self-activated carbon for adsorptive removal of toxic phenoxyacetic acid herbicide from water.

Phenoxyacetic acid herbicides are widely used in agriculture for controlling weeds. These organic compounds are persistent and recalcitrant, often contaminating water and soil. Therefore, we studied five pristine biochars (BCs), and southern yellow pine (SYP) based self-activated carbon (SAC) for the adsorptive removal of 2,4-Dichlorophenoxyacetic acid (2,4-D) herbicide. Among the tested adsorbents, SYP-SAC-15 demonstrated higher (>90%) 2,4-D removal from water. The SYP-SAC-15 was produced using a facile and green route where the biomass pyrolysis gases worked as activating agents creating a highly porous structure with a surface area of 1499.79 m2/g. Different adsorption kinetics and isotherm models were assessed for 2,4-D adsorption on SYP-SAC-15, where the data fitted best to pseudo-second order (R2 > 0.999) and Langmuir (R2 > 0.991) models, respectively. Consequently, the adsorption process was mainly dominated by the chemisorption mechanism with monolayer coverage of SYP-SAC-15 surface with 2,4-D molecules. At the optimum pH of 2, the maximum 2,4-D adsorption capacity of SYP-SAC-15 reached 471.70 mg/g. Furthermore, an increase in the water salinity demonstrated a positive influence on 2,4-D adsorption, whereas humic acid (HA) showed a negative impact on 2,4-D adsorption. The regeneration ability of SYP-SAC-15 showed excellent performance by retaining 71.09% adsorption capability at the seventh adsorption-desorption cycle. Based on the operating pH, surface area, spectroscopic data, kinetics, and isotherm modeling, the adsorption mechanism was speculated. The 2,4-D adsorption on SYP-SAC-15 was mainly governed by pore filling, electrostatic interactions, hydrogen bonding, hydrophobic and π-π interactions.

Enhanced adsorption of 2,4-dichlorophenoxyacetic acid using low-temperature carbonized Peltophorum pterocarpum pods and its statistical physics modeling.

The usage of various herbicides in the agricultural field leads to water pollution which is a big threat to the environment. Herein, the pods of the Peltophorum pterocarpum tree were used as a cheap resource to synthesize activated carbon (AC) by low-temperature carbonization to remove 2,4-dichlorophenoxyacetic acid (2,4-D) - an abundantly used herbicide. The exceptional surface area (1078.34 m2/g), mesoporous structure, and the various functional groups of the prepared AC adsorbed 2,4-D effectively. The maximum adsorption capacity was 255.12 mg/g, significantly higher than the existing AC adsorbents. The adsorption data satisfactorily modelled using Langmuir and pseudo-second-order models. Also, the adsorption mechanism was studied using a statistical physics model which substantiated the multi-molecular interaction of 2,4-D with the AC. The adsorption energy (<20 kJ/mol) and thermodynamic studies (ΔH°: -19.50 kJ/mol) revealed the physisorption and exothermicity. The practical application of the AC was successfully tested in various waterbodies by spiking experiments. Hence, this work confirms that the AC prepared from the pods of P. pterocarpum can be applied as a potential adsorbent to remove herbicides from polluted waterbodies.

Valorization of date palm leaves for adsorptive remediation of 2,4-dichlorophenoxyacetic acid herbicide polluted agricultural runoff.

Alarming rates of water contamination by toxic herbicides have prompted the need and attention for easy, efficient, and affordable treatment options with a touch of circular economy aspects. This study valorized date palm leaf (DPL) wastes into a valuable adsorbent for remediating agricultural wastewater polluted with 2,4-Dichlorophenoxyacetic acid (2,4-DPA) herbicide. The DPL precursor was modified with H2SO4 treatment and both biomass samples were characterized by various analytical techniques. Acid treatment modified the morphology, thermal, and textural properties of the final product (TDPL) while maintaining the structure and surface chemistry intact. Simulated wastewaters containing 2,4-DPA were subsequently treated using TDPL as an adsorbent. Optimum adsorption conditions of pH 2, dosage 0.95 g/L, shaking speed 200 rpm, time 120 min, and temperature 30 °C showed a good herbicide removal efficiency in the range of 55.1-72.6% for different initial feed concentrations (50-250 mg/L). Experimental kinetic data were better represented by the pseudo-second-order model, while the Freundlich isotherm was reliable in describing the equilibrium behavior of the adsorption system. Further, the thermodynamic analysis revealed that the adsorption occurred spontaneously, favorably, and exothermically. Plausible sorption mechanism involved electrostatic interactions, weak van der Waals forces, hydrogen bonds, and π-π interactions between the participating phases. Conspicuously, TDPL application to real-world situations of treating actual herbicide-polluted agricultural runoff resulted in a 69.4% remediation efficiency. Thus, the study demonstrated the valorization of date palm leaves into a valuable and industry-ready adsorbent that can sequester toxic 2,4-DPA herbicide contaminant from aqueous streams.

Supramolecular Self-Assembly of Herbicides with Reduced Risks to the Environment.

The side effects caused by some pesticides with high off-target movement have brought great risks to the environment and human health. Here, taking 2,4-dichlorophenoxyacetic acid (2,4-D) as a model herbicide to reduce its volatilization and leaching, a supramolecular self-assembly mediated by branched polyethylenimine (B-PEI) was constructed through noncovalent molecular recognition. The results showed that 2,4-D/B-PEI nanoparticles (NPs) with a mean particle size of 168 nm can be formed by electrostatic interaction, hydrophobic effect, and π-π stacking when the mass ratio of 2,4-D to B-PEI with the average molecular weight of 10 000 (B-PEI 10k) was 40:20, and their generation was not susceptible to common inorganic ions such as Ca2+, Na+, Cl-, and SO42-. Compared with 2,4-D, the self-assembled NPs with improved physicochemical properties including strong positive charges (+58.2 mV), reduced volatilization rate (2.50%), low surface tension (56.10 mN m-1), and decreased leaching potential could minimize the adverse impacts of this herbicide on the environment. The biological activity experiments in the greenhouse and field demonstrated that the control efficacy of NPs without using any surfactant against weeds was almost the same as that of the 2,4-D sodium salt form containing Tween 80. The safety tests showed that the self-assembled NPs had the same genotoxicity as 2,4-D to Vicia faba and little effect on the soil enzyme activities. Overall, the development of self-assembled herbicidal nanoformulations with desirable physicochemical properties and low risks to the environment would have potential application in agricultural production.

Development of a Rapid Gold Nanoparticle Immunochromatographic Strip Based on the Nanobody for Detecting 2,4-DichloRophenoxyacetic Acid.

2,4-Dichlorophenoxyacetic acid (2,4-D) is a systemic conductive herbicide widely used across the world. With the large-scale and continuous use of 2,4-D, its possible harm to the environment and non-target organisms has attracted increasing attention, and the construction of a stable rapid on-site detection method is particularly important. In order to achieve on-site rapid detection of 2,4-D, we developed a gold nanoparticle immunochromatographic strip method with the visual elimination value was 50 ng/mL, and a quantitative detection limit of 11 ng/mL based on a nanobody. By combing with the color snap, the immunochromatographic strip could quantitatively analyze the amounts of 2,4-D. Meanwhile, a colorimetric card based on the true color of the test strips was developed for the qualitative analysis of 2,4-D on-site. The samples (water, fruits and vegetables) with and without 2,4-D were detected by the immunochromatographic strips, and the results showed the accuracy and reliability. Thus, this assay is a rapid and simple on-site analytical tool to detect and quantify 2,4-D levels in environmental samples, and the analytical results can be obtained in about ten minutes. In addition, the nanobody technology used in this study provides an inexhaustible supply of a relatively stable antibodies that can be archived as a nanobody, plasmid or even its sequence.

One step acid modification of the residual bark from Campomanesia guazumifolia using H2SO4 and application in the removal of 2,4-dichlorophenoxyacetic from aqueous solution.

The residual bark of the tree species Campomanesia guazumifolia was successfully modified with H2SO4 and applied to remove the toxic herbicide 2.4-dichlorophenoxyacetic (2.4-D) from aqueous solutions. The characterization techniques made it possible to observe that the material maintained its amorphous structure; however, a new FTIR band emerged, indicating the interaction of the lignocellulosic matrix with sulfuric acid. Micrographs showed that the material maintained its irregular shape; however, new spaces and cavities appeared after the acidic modification. Regardless of the herbicide concentration, the system tended to equilibrium after 120 min. Using the best statistical coefficients, the Elovich model was the one that best fitted the kinetic data. The temperature increase in the system negatively influenced the adsorption of 2.4-D, reaching a maximum capacity of 312.81 mg g-1 at 298 K. The equilibrium curves showed a better fit to the Tóth model. Thermodynamic parameters confirmed the exothermic nature of the system (ΔH0 = -59.86 kJ mol-1). As a residue obtained from urban pruning, the bark of Campomanesia guazumifolia treated with sulfuric acid is a promising and highly efficient alternative for removing the widely used and toxic 2.4-D herbicide from aqueous solutions.

Multiple Gene Clusters and Their Role in the Degradation of Chlorophenoxyacetic Acids in Bradyrhizobium sp. RD5-C2 Isolated from Non-Contaminated Soil.

Bradyrhizobium sp. RD5-C2, isolated from soil that is not contaminated with 2,4-dichlorophenoxyacetic acid (2,4-D), degrades the herbicides 2,4-D and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). It possesses tfdAα and cadA (designated as cadA1), which encode 2,4-D dioxygenase and the oxygenase large subunit, respectively. In the present study, the genome of Bradyrhizobium sp. RD5-C2 was sequenced and a second cadA gene (designated as cadA2) was identified. The two cadA genes belonged to distinct clusters comprising the cadR1A1B1K1C1 and cadR2A2B2C2K2S genes. The proteins encoded by the cad1 cluster exhibited high amino acid sequence similarities to those of other 2,4-D degraders, while Cad2 proteins were more similar to those of non-2,4-D degraders. Both cad clusters were capable of degrading 2,4-D and 2,4,5-T when expressed in non-2,4-D-degrading Bradyrhizobium elkanii USDA94. To examine the contribution of each degradation gene cluster to the degradation activity of Bradyrhizobium sp. RD5-C2, cadA1, cadA2, and tfdAα deletion mutants were constructed. The cadA1 deletion resulted in a more significant decrease in the ability to degrade chlorophenoxy compounds than the cadA2 and tfdAα deletions, indicating that degradation activity was primarily governed by the cad1 cluster. The results of a quantitative reverse transcription-PCR analysis suggested that exposure to 2,4-D and 2,4,5-T markedly up-regulated cadA1 expression. Collectively, these results indicate that the cad1 cluster plays an important role in the degradation of Bradyrhizobium sp. RD5-C2 due to its high expression.

Micropropagation and Secondary Metabolites Content of White-Purple Varieties of Orthosiphon aristatus Blume Miq.

<b>Background and Objective:</b> The cat whiskers plant (<i>Orthosiphon aristatus</i> Blume Miq) is a plant that has been widely used as raw material for traditional medicine. The population of white-purple varieties of <i>O. aristatus</i> is decreasing efforts to maintain the white-purple <i>O. aristatus</i> need to be done keeping in mind its potential as raw material for traditional medicine. This study aims to determine the composition of a suitable medium in growing plantlet <i>O. aristatus</i> white-purple varieties and the content of its secondary metabolites. <b>Materials and Methods:</b> The internode explants were induced on MS medium added by various combinations of zeatin and 2,4-Dichlorophenoxyacetic acid (2,4-D). Root induction was carried out on shoots formed on MS medium with Indole-3-Butyric Acid (IBA). The acclimatization process was carried out using soil media. Determination of secondary metabolite levels was carried out on <i>O. aristatus</i> (<i>in vitro</i> culture) and wild-type plants aged ten months using high-performance liquid chromatography (HPLC). <b>Results:</b> MS+BAP 2ppm+NAA3 ppm media was the optimal medium for growing shoots in leaf explants. Media MS+zeatin 3 ppm+2,4-D 2 ppm produced good shoot growth on internode explants. The best root induction occurred in MS+IBA media of 0.75 ppm. The acclimatization process was successful on shoots originating from the internode, while those from leaf explants had not succeeded in growing and developing. <b>Conclusion:</b> The levels of rosmarinic acid and sinensetin in the white-purple variety <i>O. aristatus</i> (<i>in vitro</i> culture) were 1.08 and 1.62% w/w and higher than those of wild varieties.

Nanomaterials for Targeted Delivery of Agrochemicals by an All-in-One Combination Strategy and Deep Learning.

The development of modern agriculture has prompted the greater input of herbicides, insecticides, and fertilizers. However, precision release and targeted delivery of these agrochemicals still remain a challenge. Here, a pesticide-fertilizer all-in-one combination (PFAC) strategy and deep learning are employed to form a system for controlled and targeted delivery of agrochemicals. This system mainly consists of three components: (1) hollow mesoporous silica (HMS), to encapsulate herbicides and phase-change material; (2) polydopamine (PDA) coating, to provide a photothermal effect; and (3) a zeolitic imidazolate framework (ZIF8), to provide micronutrient Zn2+ and encapsulate insecticides. Results show that the PFAC at concentration of 5 mg mL-1 reaches the phase transition temperature of 1-tetradecanol (37.5 °C) after 5 min of near-infrared (NIR) irradiation (800 nm, 0.5 W cm-2). The data of corn and weed are collected and relayed to deep learning algorithms for model building to realize object detection and further targeted weeding. In-field treatment results indicated that the growth of chicory herb was significantly inhibited when treated with the PFAC compared with the blank group after 24 h under NIR irradiation for 2 h. This system combines agrochemical innovation and artificial intelligence technology, achieves synergistic effects of weeding and insecticide and nutrient supply, and will potentially achieve precision and sustainable agriculture.

Fabrication of gelatin microspheres containing ammonium hydrogen carbonate for the tunable release of herbicide.

The major challenge in utilizing pesticides lies in identifying the precise application that would improve the efficiency of these pesticides and decline their environmental and health hazards at the same time. Such application requires the development of specific formulations that enable controlled, stimuli-responsive release of the pesticides. Gelatin is a relatively cheap material characterized by temperature-sensitivity and abundant amino acid groups, which makes it suitable for the storage and controlled release of pesticides. In this study, gelatin microspheres were prepared by emulsion and cross-linking, then they were loaded with 2,4-dichlorophenoxyacetic acid sodium (2,4-D Na) as a model herbicide. To achieve temperature-tunable release of 2,4-D Na from the microspheres, NH4HCO3 was added to the formulations at different concentrations. The prepared formulations were characterized by SEM, FTIR, and size distribution analyzes, and their drug loading capacities were determined. Based on bioassay experiments, the 2,4-D Na-NH4HCO3-loaded gelatin microspheres can effectively control the spread of dicotyledonous weeds. Therefore, the strategy proposed herein can be used to develop novel, effective herbicide formulations.

Shoot Multiplication and Callus Induction of Labisia pumila var. alata as Influenced by Different Plant Growth Regulators Treatments and Its Polyphenolic Activities Compared with the Wild Plant.

This study aims to investigate whether the in vitro-cultured L. pumila var. alata has higher antioxidant activity than its wild plant. An 8-week-old L. pumila var. alata nodal segment and leaf explants were cultured onto Murashige and Skoog (MS) medium supplemented with various cytokinins (zeatin, kinetin, and 6-benzylaminopurine (BAP)) for shoot multiplication and auxins (2,4-dichlorophenoxyacetic acid (2,4-D) and picloram) for callus induction, respectively. The results showed that 2 mg/L zeatin produced the optimal results for shoot and leaf development, and 0.5 mg/L 2,4-D produced the highest callus induction results (60%). After this, 0.5 mg/L 2,4-D was combined with 0.25 mg/L cytokinins and supplemented to the MS medium. The optimal results for callus induction (100%) with yellowish to greenish and compact texture were obtained using 0.5 mg/L 2,4-D combined with 0.25 mg/L zeatin. Leaves obtained from in vitro plantlets and wild plants as well as callus were extracted and analyzed for their antioxidant activities (DPPH and FRAP methods) and polyphenolic properties (total flavonoid and total phenolic content). When compared with leaf extracts of in vitro plantlets and wild plants of L. pumila var. alata, the callus extract displayed significantly higher antioxidant activities and total phenolic and flavonoid content. Hence, callus culture potentially can be adapted for antioxidant and polyphenolic production to satisfy pharmaceutical and nutraceutical needs while conserving wild L. pumila var. alata.

Renewable and robust biomass waste-derived Co-doped carbon aerogels for PMS activation: Catalytic mechanisms and phytotoxicity assessment.

Developing monolithic carbon-based catalyst with low cost, easy separation and high performance to degrade pollutants via PMS activation is crucial. In this work, a series of novel monolithic Me-CA catalysts based on biomass derived carbon aerogel were prepared by hydrothermal method using waste watermelon peel as raw material. Co-CA catalyst showed excellent performance to activate PMS for 2, 4-DCP degradation in different temperature and different water matrices. Different pollutants, such as ciprofloxacin (CIP), bisphenol A (BPA), and 2, 4-dichlorophenoxyacetic acid (2, 4-D) could also be removed in the Co-CA/PMS system. As expected, Co-CA could be easily separated from degraded solution, and show high stability and reusability for PMS activation with a lower cobalt leaching. Based on the results of the quenching tests, electron paramagnetic resonance (EPR) spectra, Chronoamperometric test (i-t curves) and electro-chemical impedance spectroscopy (EIS), the PMS activation mechanism was proposed. The phytotoxicity assessment determined by germination situation of mung bean indicated that PMS activation could eliminate the hazards of 2, 4-D. Therefore, this study provides a low cost, efficient and environmental-friendly monolithic biomass carbon aerogel catalyst for different pollutants degradation, which further advances monolithic catalyst for practical wastewater treatment.

Biochemical Characterization of Recombinant UDPG-Dependent IAA Glucosyltransferase from Maize (Zea mays).

Here, we report a biochemical characterization of recombinant maize indole-3-acetyl-ß-d-glucose (IAGlc) synthase which glucosylates indole-3-acetic acid (IAA) and thus abolishes its auxinic activity affecting plant hormonal homeostasis. Substrate specificity analysis revealed that IAA is a preferred substrate of IAGlc synthase; however, the enzyme can also glucosylate indole-3-butyric acid and indole-3-propionic acid with the relative activity of 66% and 49.7%, respectively. KM values determined for IAA and UDP glucose are 0.8 and 0.7 mM, respectively. 2,4-Dichlorophenoxyacetic acid is a competitive inhibitor of the synthase and causes a 1.5-fold decrease in the enzyme affinity towards IAA, with the Ki value determined as 117 µM, while IAA-Asp acts as an activator of the synthase. Two sugar-phosphate compounds, ATP and glucose-1-phosphate, have a unique effect on the enzyme by acting as activators at low concentrations and showing inhibitory effect at higher concentrations (above 0.6 and 4 mM for ATP and glucose-1-phosphate, respectively). Results of molecular docking revealed that both compounds can bind to the PSPG (plant secondary product glycosyltransferase) motif of IAGlc synthase; however, there are also different potential binding sites present in the enzyme. We postulate that IAGlc synthase may contain more than one binding site for ATP and glucose-1-phosphate as reflected in its activity modulation.

Impact of dichlorprop on soil microbial community structure and diversity during its enantioselective biodegradation in agricultural soils.

Enantioselective biodegradation of racemic dichlorprop in two soils was investigated in the laboratory. Chiral separation of racemic dichlorprop was achieved by using HPLC with Phenomenex Lux Amylose-2. The first-order kinetic model fitted well the dissipation data of racemic dichlorprop and its pure R- and S-enantiomers. S-dichlorprop was preferentially degraded in both soils and enantioselectivity was affected by soil pH. The half-lives (DT50) of S-dichlorprop were 8.22 days in soil A and 8.06 days in soil D, while R-dichlorprop was more persistent with DT50 of 12.93 days in soil A and 12.38 days in soil D, respectively. Dichlorprop dissipated faster in soil D with lower organic matter content. In sterilized soils, neglected dissipation was observed and enantiomer fraction values remained constant, indicating that the enantioselective degradation was mainly controlled by soil microorganisms. Soil microbial community structure and diversity was assessed by Illumina MiSeq sequencing of 16S rRNA genes from dichlorprop and no dichlorprop contaminated microcosms. Compared with controls, dichlorprop application had no significant effect on microbial community structures at phylum level, but increased bacterial diversity and dichlorprop degradation related taxa in both soils. S-dichlorprop preferential degradation might be attributed to the S-enantiomer preferred degraders in the family of Sphingomonadaceae.

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.

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.

Enantioselective Catabolism of the Two Enantiomers of the Phenoxyalkanoic Acid Herbicide Dichlorprop by Sphingopyxis sp. DBS4.

Dichlorprop [(RS)-2-(2,4-dichlorophenoxy)propanoic acid; DCPP], an important phenoxyalkanoic acid herbicide (PAAH), is extensively used in the form of racemic mixtures (Rac-DCPP), and the environmental fates of both DCPP enantiomers [(R)-DCPP and (S)-DCPP] mediated by microorganisms are of great concern. In this study, a bacterial strain Sphingopyxis sp. DBS4 was isolated from contaminated soil and was capable of utilizing both (R)-DCPP and (S)-DCPP as the sole carbon source for growth. Strain DBS4 preferentially catabolized (S)-DCPP as compared to (R)-DCPP. The optimal conditions for Rac-DCPP degradation by strain DBS4 were 30 °C and pH 7.0. In addition to Rac-DCPP, other PAAHs such as (RS)-2-(4-chloro-2-methylphenoxy)propanoic acid, 2,4-dichlorophenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid, and 2,4-dichlorophenoxyacetic acid butyl ester could also be catabolized by strain DBS4. Bioremediation of Rac-DCPP-contaminated soil by inoculation of strain DBS4 exhibited an effective removal of both (R)-DCPP and (S)-DCPP from the soil. Due to its broad substrate spectrum, strain DBS4 showed great potential in the bioremediation of PAAH-contaminated sites.

High-performance of activated biocarbon based on agricultural biomass waste applied for 2,4-D herbicide removing from water: adsorption, kinetic and thermodynamic assessments.

Activated biocarbons were prepared using biomass wastes: sugarcane bagasse, coconut shell and endocarp of babassu coconut; as a renewable source of low-cost raw materials and without prior treatments. These activated biocarbons were characterized by textural analysis, solid-state 13C nuclear magnetic resonance spectroscopy, X-ray diffraction and scanning electronic microscopy. Textural analysis results revealed that those activated biocarbons were microporous, with specific surface area values of 547, 991 and 1,068 m2 g-1 from sugarcane bagasse, coconut shell and endocarp of babassu coconut, respectively. The innovation of this work was to evaluate which biomass residue was able to offer the best performance in removing 2,4-dichlorophenoxyacetic acid herbicide (2,4-D) from water by adsorption. Adsorption process of 2,4-D was investigated and the Langmuir and Redlich-Peterson models described best the adsorption process, with R2 values within 0.96-0.99. The 2,4-D removal performance were 97% and 99% for the coconut and babassu biocarbons, respectively. qM parameter values obtained from Langmuir model were 153.9, 233.0 and 235.5 mg g-1 using sugarcane bagasse, coconut shell and endocarp of babassu, respectively. In addition, the adsorption kinetics were described nicely by the second-order model and the Gibbs free energy parameter values were negative, pointing to a spontaneous adsorption, as well.