Na-alginate,polyaniline and polypyrrole composites with cellulosic biomass for the adsorptive removal of herbicide: Kinetics,equilibrium and thermodynamic studies

This study was designed to prepare the sugarcane bagasse (SB) composite with polyaniline (PAn), polypyrrole (Ppy) and sodium alginate (NaA) and employed as an adsorbent for the adsorptive removal of herbicide (2,4-dicholorophenoxyacetic acid, 2,4-D). Fabricated composites were characterized by SEM and FTIR techniques. The affecting variables, i.e., temperature, contact time, initial herbicide concentration, medium pH and adsorbent dose were studied in batch mode. Different isotherms were employed on the adsorption data and the maximum adsorption capacity of SB was recorded to be 77.75 mg/g at pH 3.0, 150 mg/L 2,4-D initial concentration at 30 °C. The models (pseudo-second-order and Freundlich) best explained the adsorption experimental data with R² values ≥ 0.90 and ≥ 0.96, respectively. The thermodynamics parameters (ΔG, ΔH, and ΔS) were computed and the herbicide adsorption onto the composites was an exothermic and spontaneous process. Results revealed that sugarcane bagasse composites with PAn, Ppy, and NaA are efficient adsorbents, which could be used for the remediation of 2,4-D in the effluents.     

Regenerable immunobiosensor for the chemiluminescent flow injection analysis of the herbicide 2,4-D

A semi-automated chemiluminescent competitive immunosensor for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) is presented. Anti-2,4-D polyclonal antibodies are directly labelled with horseradish peroxidase allowing a p-iodophenol enhanced chemiluminescent detection. Using antigen immobilised on UltraBind type pre-activated membranes, the 2,4-D immunosensor exhibits low non-specific/specific binding ratio (maximum ratio: 5%) of the labelled antibodies. The quantification of free 2,4-D in water is performed by co-injecting the sample and the labelled antibodies in the flow system, incubating this solution with the antigen immobilised membrane and measuring the amount of specifically bound labelled antibodies. Such an analytical system enables the detection of 4 mug l(-1) of free antigen in 20 min, and the 2,4-D detection is possible in the range 4 mug l(-1)-160 mg l(-1). The immunosensor can be regenerated by simply flowing a chaotropic solution (0.1 M HCl, 0.1 M NaCl, 0.1 M glycine) in the system. This regeneration ability enables the achievement of more than 30 measurement cycles of free 2,4-D with the same antigen immobilised membrane with a good reproducibility (RSD=12.5%).     

Dechlorination of 2,4-dichlorophenoxyacetic acid using biochar-supported nano-palladium/iron: Preparation,characterization, and influencing factors

In the present study, peanut shell, a green waste raw material, was used to prepare biochar (BC) and to obtain BC-supported nano-palladium/iron (BC-nPd/Fe) composites for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from water. Characterization analysis demonstrated that nPd/Fe particles were well dispersed on the BC surface with weakened magnetic properties. The average particle diameter and specific surface area of nPd/Fe were 101.3 nm and 6.7 m² g⁻¹, whereas the corresponding values of the BC-nPd/Fe materials were 88.8 nm and 14.8 m² g⁻¹, respectively. Several factors were found to influence the dechlorination of 2,4-D, including the weight ratio of BC to Fe, Pd loading ratio, initial solution pH, 2,4-D concentration, and reaction temperature. Dechlorination results indicated that the 2,4-D removal and phenoxyacetic acid (PA) generation rates were 44.1% and 20.1%, respectively, in the nPd/Fe system, and 100.0% and 92.1%, respectively, in the BC-nPd/Fe system. The dechlorination of 2,4-D was well described by the pseudo-first-order kinetic model (R² > 0.97), and the observed rate constants k_obs were 0.0042 min (nPd/Fe) and 0.0578 min (BC-nPd/Fe), respectively. The reaction mechanism indicated that the dechlorination hydrogenation was the main process to remove 2,4-D from water in the BC-nPd/Fe system. In addition, BC inhibited the formation of a passivation layer on the particle surface during the reaction, thus maintaining the high reactivity of BC-nPd/Fe. The easy preparation technique, high 2,4-D dechlorination capacity, and mild reaction conditions suggest that BC-nPd/Fe may be a promising alternative composite to remove 2,4-D from water.     

Amperometric Immunosensor for the Detection of 2,4-Dichlorophenoxyacetic Acid (2,4-D) in Water

ABSTRACT

An amperometric immunosensor for the determination of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in water has been developed using sequential injection analysis techniques. The system is based on a rapid competitive enzyme immunoassay employing an alkaline phosphatase-labeled monoclonal antibody directed against the herbicide and an immunoreactor with 2,4-D immobilized via bovine serum albumin either to Eupergit in a column or directly to the surface of a glass capillary. The detection limit of the immunosensor at 0.1 μg 2,4-D/l without enrichment of the analyte makes automatic measurements of 2,4-D in drinking and ground water feasible.     

Mechanism of hydroxyl radical-induced breakdown of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-d)

Oxidative transformations by the hydroxyl radical are significant in advanced oxidation processes for the breakdown of organic pollutants, yet mechanistic details of the reactions are lacking. A combination of experimental and computational methods has been employed in this study to elucidate the reactivity of the hydroxyl radical with the widely used herbicide 2,4-D (2,4-dichlorophenoxyacetic acid). The experimental data on the reactivity of the hydroxyl radical in the degradation of the herbicide 2,4-D were obtained from gamma-radiolysis experiments with both (18)O-labeled and unlabeled water. These were complemented by computational studies of the (.)OH attack on 2,4-D and 2,4-DCP (2,4-dichlorophenol) in the gas phase and in solution. These studies firmly established the kinetically controlled attack ipso to the ether functionality as the main reaction pathway of (.)OH and 2,4-D, followed by homolytic elimination of the ether side chain. In addition, the majority of the early intermediates in the reaction between the hydroxyl radical and 2,4-DCP, the major intermediate, were identified experimentally. While the hydroxyl radical attacks 2,4-D by (.)OH-addition/elimination on the aromatic ring, the oxidative breakdown of 2,4-DCP occurs through (.)OH addition followed by either elimination of chlorine or formation of the ensuing dichlorophenoxyl radical.     

Immunodetection of Herbicide 2,4-Dichlorophenoxyacetic Acid by Field-Effect Transistor-Based Biosensors

Abstract

An immunosensor method for determination of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was developed. It is based on the use of the competition between 2,4-D in analyzed probes and 2,4-D-peroxidase conjugate for binding with antibodies being immobilized on porous photo-activated cellulose membranes. These membranes were attached to the gate region of pH-sensitive field transistor (FET) and electrochemical detection of enzyme activity was carried out. Mixture of ascorbic acid (0.1 mM), o-phenylenediamine (1.0 mM), hydrogen peroxide (1.0 mM) was used as substrate solution. The initial rate of pH-shift of the FETs gate region was recorded as measured parameter.

The developed system permits to determine 2,4-D in water solutions for concentrations down to 1 ng/ml. This portable and inexpensive immunosensor meets modern requirements as analytical system for ecological monitoring.     

Electrochemical investigation of the interaction of 2,4-D and double stranded DNA using pencil graphite electrodes

2,4-dichlorophenoxyacetic acid (2,4-D) is an auxinic herbicide used to control broadleaf weeds. It is also a threatening factor for not only aquatic life but also human health due to its genotoxicity and endocrine disruptive property. Herein, the interaction between 2,4-D and double stranded DNA was investigated by using single-use pencil graphite electrodes (PGE) in combination with electrochemical techniques. The detection mechanism was based on the monitoring of the changes at the guanine oxidation signal obtained before/after surface-confined interaction of 2,4-D and DNA at the surface of PGE. The electrochemical characterization of the interaction was studied by using microscopic and electrochemical techniques. The response obtained by interaction in the presence of another herbicide, glyphosate, which is widely used with 2,4-D for weed control, was compared to the one occurred in the presence of 2,4-D. Electrochemical monitoring of the interaction between the herbicide whose active molecule was 2,4-D and DNA was also investigated. The detection (LOD) and quantification limits (LOQ) for 2,4-D and the herbicide could be obtained in the linear concentration ranges of 30–70 µg/mL and 10–30 µg/mL, respectively and LOD and LOQ values were found to be 2.85 and 9.50 µg/mL for both 2,4-D and the herbicide. The sensitivity of the biosensor was calculated as 0.087 µA.mL / µg.cm² .This is the first study in literature by means of not only voltammetric detection of 2,4-D and DNA interaction but also the herbicide-DNA interaction at the surface of PGE based on the changes at the guanine signal.     

Disposable multichannel immunosensors for 2,4-dichlorophenoxyacetic acid using acetylcholinesterase as an enzyme label

An improved version of the disposable multichannel immunochemical biosensor for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) based on a screen-printed amperometric transducer and monoclonal antibodies (MAb) against 2,4-D is reported. Entrapment within a thin Nafion film was used for the direct immobilization of MAb at the electrode surface. The amount of the tracer (2,4-D conjugated to acetylcholinesterase) bound in a competitive immunochemical reaction was determined amperometrically using acetylthiocholine iodide as substrate. The measuring procedure (times of incubation with tracer and substrate, pH, tracer concentration) was optimized. The sensor was able to detect less than 0.01 μg/L of free 2,4-D in water. One analysis (8 samples) was completed in 30 min (20 min for immunochemical reaction, 5 min incubation with substrate, 5 min measurement). The performance of the immunosensor (two configurations) was evaluated on real samples (tap water) with added 2,4-D. The determined amounts (mean values 0.097 to 0.105 and 0.89 to 1.13) corresponded well with the added contents of 2,4-D (0.100 and 1.00 μg/L, respectively).     

The removal of chlorinated organic herbicide in water by gamma-irradiation

In this study, the radiation-induced degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide in aqueous solution was studied under various conditions as a function of irradiation dose in the absence and presence of hydrogen peroxide. The obtained data confirmed that largest yield of radiolytic degradation is obtained in oxidation processes/ionizing radiation, where oxidation is carried out with hydroxyl radicals. For complete degradation of 50?ppm 2,4-D, a required dose was lower in the presence of hydrogen peroxide. The formed major toxic phenolic intermediates were 2,4-dichlorophenol (2,4-DCP) and 4-chlorophenol (4-CP). The chemical analysis of the 2,4-D and the intermediates resulted from the radiolytic degradation were performed using a gas chromatography associated to mass spectrometry (GC?CMS) with ion trap dedector (ITD) and ion chromatography (IC). The formation of chlorophenols in addition to chloride, formaldehyde and carboxylic acids was studied as a function of absorbed dose.     

Gold nanoparticles catalyzed chemiluminescence immunoassay for detection of herbicide 2,4-dichlorophenoxyacetic acid

We present a novel immunoassay format utilizing the catalytic properties of gold nanoparticles in the luminol-silver nitrate-gold nanoparticle based chemiluminescence (CL) system for the detection of widely used herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Highly sensitive anti-2,4-D antibody was produced and conjugated with gold nanoparticles of various sizes. In the present assay format, employing a competitive inhibition approach, a well-characterized hapten-protein conjugate (2,4-D-BSA) was used to coat the microtiter plates. The analyte (2,4-D) was pre-incubated with anti-2,4-D antibody labeled with gold nanoparticles and added to each well of the microtiter plate. The gold label triggered the reaction between luminol and silver nitrate generating a luminescence signal at 425 nm. Under the optimized conditions, the CL based immunoassay showed the detection limit of 2,4-D in standard water samples around 3 ng mL(-1). The CL based immunoassay format, based on gold nanoparticles as a catalyst, could be used as a fast screening methodology (<30 min) for pesticide detection.     

Adsorption and preconcentration of 2,4-dichlorophenoxyacetic acid on a chemically modified silica gel surface

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), chemically anchored to a silica gel surface, was used to adsorb and preconcentrate the same herbicide from aqueous solutions at room temperature. From a series of adsorption isotherms adjusted to a modified Langmuir equation, the maximum number of moles adsorbed was calculated as 4.67 x 10(-5) mol g(-1), with the highest retention capacity at pH 5. This modified silica gel was used in a column for preconcentrating trace levels of 2,4-D. The preconcentrated herbicide can be directly eluted with methanol with a recovery efficiency higher than 97%. The concentration factor was 8.33.     

Removal of 2,4-dichlorophenoxyacetic acid from aqueous solutions by partially characterized organophilic sepiolite: thermodynamic and kinetic calculations

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on organophilic sepiolite (dodecylammonium sepiolite, DAS) was studied as a function of solution concentration and temperature. The observed adsorption rates were found to be equal to the first-order kinetics. The rate constants were calculated for temperatures ranging between 25 and 40 degrees C at constant concentration. The adsorption energies, E, and adsorption capacity, q(m), for 2,4-D adsorption on organophilic sepiolite was estimated using the Dubinin-Radushkevic equation. Thermodynamic parameters (Deltag(a), Deltah(a), Deltas(a)) were determined by a new approximation from the isotherm of 2,4-D adsorption on DAS. Also, DeltaS(0) and DeltaH(0) values were calculated from the van't Hoff equation. These isotherms were modeled according to the Freundlich and Dubinin-Radushkevic adsorption equations. The amount of adsorption of this herbicide on organophilic sepiolite was found to be dependent on the relative energies of adsorbent-adsorbate, adsorbate-solvent, and adsorbate-adsorbate interaction.     

pH-dependent release from ethylcellulose microparticles containing alginate and calcium carbonate

Ethylcellulose microparticles containing alginate and calcium carbonate nanoparticles were prepared by spray drying water-in-oil emulsion. Alginate solution (3%) in distilled water was used as an aqueous phase, ethylcellulose solution (5%) in dichloromethane as an oil phase, and sorbitan sesquioleate as an emulsifier. The nanoparticles of calcium carbonate were dispersed into the emulsion. By spray-drying the emulsion, ethylcellulose microparticles containing alginate and calcium carbonate were obtained. When the ratios of alginate to calcium carbonate were 4:1 and 2:1, the pH dependency of the release was marked and the degree of release was suppressed in acidic conditions. When the ratio increased to 1:2, the degree of release increased while the pH-dependent release profiles were maintained. Cavities created by the dissolution of calcium carbonate could account for the increased release.     

Molecular recognition in imprinted polymers: thermodynamic investigation of analyte binding using microcalorimetry

This study aimed at elucidating the interaction mechanism between an imprinted polymer and its template in aqueous environment with thermodynamic aspects. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was chosen as a model template to imprint a co-polymer of 4-vinylpyridine (4-VP) and ethyleneglycol dimethacrylate. Equilibrium binding isotherm analysis and isothermal titration microcalorimetry were used to quantify the contribution of enthalpy and entropy to the binding process, identify the nature of the interactions involved and confirm the existence of binding pockets with shape-complementarity to the template. For the binding process of 2,4-D to the imprinted polymer, we postulate three subprocesses: (1) dehydration of the binding pocket and of the 2,4-D, (2) adsorption of 2,4-D, and (3) rearrangement of the water molecules from the dehydration process. We found that binding in aqueous environment was due to the cumulative effect of pi-stacking and electrostatic interactions between the template and the functional monomers. At pH<6, entropy is the dominating driving force, while at pH>6 where the highest difference in binding between the imprinted and a non-imprinted reference polymer was observed, the enthalpy change accounts for most of the binding free energy. The developed microcalorimetric method sheds light on the binding mechanism of analyte molecules with imprinted polymers, in particular if the polymers are used in aqueous solvents.     

Molecularly imprinted polypyrrole nanonecklaces for detection of herbicide through molecular recognition-amplifying current response

Molecularly imprinted polypyrrole (PPy) nanonecklaces were facilely synthesized through a two-step oxidative polymerization route for the amperometric detection of non-electrochemically active herbicide. It has been demonstrated that dissolved oxygen can preoxidize pyrrole to form PPy oligomer bundles, which further self-assemble into necklace-like micelles in the presence of cetyltrimethylammonium bromide. Subsequently, these microstructures were immediately gelled through quick polymerization of residual pyrrole monomers, leading to the formation of PPy nanonecklaces. Meanwhile, herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was synchronously imprinted into the formed PPy and highly dense imprinted sites were generated in PPy nanonecklaces because the necklace-like structure with microgaps/pores provides the facile and complete removal of templates. The imprinted nanonecklaces exhibit the high capacity and fast kinetics to uptake 2,4-D molecules, and produce a imprinting factor of ∼4.2. Importantly, the recognition and binding to 2,4-D significantly amplify the current response by a factor of 8 times in amperometric measurements, providing a sensitive detection of 2,4-D. The molecular imprinting strategy opens a novel avenue to the direct detection of non-electrochemically active species in a more convenient, simpler and cheaper way than the traditional competition-displacing approaches.     

Gas-liquid chromatography and gas-liquid chromatography combined with mass spectrometry of a butyl ester formulation of (2,4-dichlorophenoxy) acetic acid.

A method is presented for the analysis of (2,4-dichlorophenoxy)acetic acid (2,4-D) in commercial formulations, together with concurrent detection and quantitation of related compounds. The method is based on direct gas-liquid chromatographic (GLC) analysis of the formulation to estimate the various esters present, and on an analysis of the total 2,4-D present involving a prior cleanup, alkaline hydrolysis, acidification and n-butylation steps. This procedure also quantitates any other related acids or phenols present. A step which would extract dioxin impurities is also included. The method was checked by the accepted acid-base estimation of 2,4-D content, GLC, and by subjecting radioactive-labelled herbicide to the above procedures.     

Fundamentals of 2, 4 Dichlorophenoxyacetic Acid Removal from Aqueous Solutions

Herbicides are widely used in farmlands worldwide. However, after their application on farmlands, they accumulate in high amounts in continental and marine waters. Herbicides are endocrine disruptors, and are known to cause toxicity, carcinogenicity and mutagenicity. Besides, they also spoil the taste and odor of water bodies. To prevent these effects, it is necessary to perform an in-depth study on various herbicide removal methods. This review discusses the various methods of herbicide removal from aqueous body, using a commonly used herbicide (2,4-dichlorophenoxyacetic acid) as a representative chemical. This paper includes a systematic tabulated review of all reported removal methods with important parameters and their mechanism. Adsorption, biological degradation, electrochemical treatment, Fenton degradation, oxidation, ozonation and photocatalytic degradation are investigated and compared for removal of 2,4-D. The advantages and disadvantages and the factors influencing selection of the aforementioned processes are discussed.     

茶多酚锰-壳聚糖微球的制备、控释和诱导肝癌细胞凋亡的研究

选用壳聚糖为微米粒包被材料, 制备茶多酚锰(Tea Polyphenol Manganese, TPMn)-壳聚糖微球. 用荧光显微技术研究了TPMn-壳聚糖微球的荧光特性, 用扫描和透射电子显微镜证实TPMn-壳聚糖微球尺寸和分布规律. RP-HPLC定量分析TPMn-壳聚糖微球包封率为68%, 符合微米级微粒控释药物包封率的要求. 动力学研究结果表明, 茶多酚(TP)-壳聚糖和TPMn-壳聚糖的微球均有控释TP的能力, 控释时间高达40 h以上, 但前者释放速率稍快于后者. TPMn和TPMn-壳聚糖微球均能诱导肝癌细胞凋亡, 但TPMn-壳聚糖微球诱导肿瘤细胞的凋亡速率稍高于TPM. 实验结果证实, 以TPMn-壳聚糖微球方式控释TPMn有利于提高诱导肿瘤细胞凋亡速率. TPMn-壳聚糖微球具有研发成注射型抗肿瘤新药的可能性.     

Isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry method for analysis of selected acidic herbicides in surface water

In this work, an isotope dilution method for determination of selected acidic herbicides by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. Average percent recoveries of native analytes were observed to be between 70.8 and 93.5% and average recoveries of labeled quantification standards [(13)C(6)]2,4-D and [(13)C(6)]2,4,5-T were 85.5 and 101%, respectively. Using this method, detection limits of 0.05 ng/L for dicamba, MCPA, MCPP, and triclopyr, and 0.5 ng/L for 2,4-D were routinely achieved. The method was applied to measuring the concentration of these analytes in surface water samples collected from five sampling locations in the Lower Fraser Valley region of British Columbia, Canada. All of the herbicides monitored were detected at varying levels in the surface water samples collected. The highest concentrations detected for each analyte were 345 ng/L for 2,4-D, 317 ng/L for MCPA, 271 ng/L for MCPP, 15.7 ng/L for dicamba, and 2.18 ng/L for triclopyr. Average detection frequencies of the herbicides were 95% for MCPA, 80% for MCPP, 70% for dicamba, 65% for 2,4-D, and 46% for triclopyr. Seasonal variations of herbicide levels are also discussed.     

High‐Temperature Spray‐Dried Polymer/Bacteria Microparticles for Electrospinning of Composite Nonwovens

Living Micrococcus luteus (M. luteus) and Escherichia coli (E. coli) are encapsulated in poly(vinyl alcohol), poly(vinylpyrrolidone), hydroxypropyl cellulose, and gelatin by high‐temperature spray drying. The challenge is the survival of the bacteria during the standard spray‐drying process at temperatures of 150 °C (M. luteus) and 120 °C (E. coli). Raman imaging and transmission electron microscopy indicate encapsulated bacteria in hollow composite microparticles. The versatility of the spray‐dried polymer bacteria microparticles is successfully proved by standard polymer solution–processing techniques such as electrospinning, even with harmful solvents, to water‐insoluble polyacrylonitrile, polystyrene, poly(methyl methacrylate), and poly(vinyl butyrate) nanofiber nonwovens, which opens numerous new opportunities for novel applications.