A Sb(III)-specific efflux transporter from Ensifer adhaerens E-60.

Antimony is pervasive environmental toxic substance, and numerous genes encoding mechanisms to resist, transform and extrude the toxic metalloid antimony have been discovered in various microorganisms. Here we identified a major facilitator superfamily (MFS) transporter, AntB, on the chromosome of the arsenite-oxidizing bacterium Ensifer adhaerens E-60 that confers resistance to Sb(III) and Sb(V). The antB gene is adjacent to gene encoding a LysR family transcriptional regulator termed LysRars, which is an As(III)/Sb(III)-responsive transcriptional repressor that is predicted to control expression of antB. Similar antB and lysRars genes are found in related arsenic-resistant bacteria, especially strains of Ensifer adhaerens, and the lysRars gene adjacent to antB encodes a member of a divergent subgroup of putative LysR-type regulators. Closely related AntB and LysRars orthologs contain three conserved cysteine residues, which are Cys17, Cys99, and Cys350 in AntB and Cys81, Cys289 and Cys294 in LysRars, respectively. Expression of antB is induced by As(III), Sb(III), Sb(V) and Rox(III) (4-hydroxy-3-nitrophenyl arsenite). Heterologous expression of antB in E. coli AW3110 (Δars) conferred resistance to Sb(III) and Sb(V) and reduced the intracellular concentration of Sb(III). The discovery of the Sb(III) efflux transporter AntB enriches our knowledge of the role of the efflux transporter in the antimony biogeochemical cycle.

Arsenic behavior in soil-plant system under the manure application with the combination of antibiotic and roxarsone.

Limited attention has been given to the interaction between antibiotics and arsenic in the soil-plant system. In this investigation, Medicago sativa seedlings were grown in soil treated with cow manure containing oxytetracycline (OTC) or sulfadiazine (SD), as well as arsenic (introduced through roxarsone, referred to as ROX treatment). The study revealed a notable increase in As(III) and dimethylarsinic acid (DMA(V)) levels in rhizosphere soils and plant root tissues as arsenic contamination intensified in the presence of antibiotics, while concentrations of As(V) and monomethylarsonic acid (MMA(V)) decreased. Conversely, elevated antibiotic presence resulted in higher levels of As(V) but reduced DMA concentrations in both rhizosphere soils and plant root tissues in the presence of arsenic. The arsenic biotransformation gene aioA was inhibited by arsenic contamination when antibiotics were present, and suppressed by antibiotic contamination in the presence of arsenic, especially in SD treatments, resulting in reduced expression levels at higher SD concentrations. Conversely, the arsM gene exhibited consistent upregulation under all conditions. However, its expression was found to increase with higher concentrations of ROX in the presence of antibiotics, decrease with increasing SD concentrations, and initially rise before declining with higher levels of OTC in the presence of arsenic. Bacterial genera within the Proteobacteria phylum, such as Geobacter, Lusitaniella, Mesorhizobium, and Methylovirgula, showed significant co-occurrence with both aioA and arsM genes. Correlation analysis demonstrated associations between the four arsenic species and the two arsenic biotransformation genes, emphasizing pH as a critical factor influencing the transformation and uptake of different arsenic species in the soil-plant system. The combined stress of antibiotics and arsenic has the potential to modify arsenic behavior and associated risks in soil-plant systems, highlighting the necessity of considering this interaction in future research endeavors.

Reusable MOF-Coated Chitosan@Paper Strip Composite for Real-Time Monitoring of Pesticide Pendimethalin and Organoarsenic Feed Additive Roxarsone Levels in Environmental Water, Food, and Vegetable Samples.

An alarming increase in the use of pesticides and organoarsenic compounds and their toxic impacts on the environment have inspired us to develop a selective and highly sensitive sensor for the detection of these pollutants. Herein, a bio-friendly, low-cost Al-based luminescent metal-organic framework (1')-based fluorescent material is demonstrated that helps in sustaining water quality by rapid monitoring and quantification of a long-established pesticide (pendimethalin) and a widely employed organoarsenic feed additive (roxarsone). A pyridine-functionalized porous aluminum-based metal-organic framework (Al-MOF) was solvothermally synthesized. After activation, it was used for fast (<10 s) and selective turn-off detection of roxarsone and pendimethalin over other competitive analytes. This is the first MOF-based recyclable sensor for pendimethalin with a remarkably low limit of detection (LOD, 14.4 nM). Real-time effectiveness in detection of pendimethalin in various vegetable and food extracts was successfully verified. Moreover, the aqueous-phase recyclable detection of roxarsone with an ultralow detection limit (13.1 nM) makes it a potential candidate for real-time application. The detection limits for roxarsone and pendimethalin are lower than the existing luminescent material based sensors. Furthermore, the detection of roxarsone in different environmental water and a wide pH range with a good recovery percentage was demonstrated. In addition, a cheap and bio-friendly 1'@chitosan@paper strip composite was prepared and successfully employed for the hands-on detection of pendimethalin and roxarsone. The turn-off behavior of 1' in the presence of pendimethalin and roxarsone was examined systematically, and plausible mechanistic pathways were proposed with the help of multiple experimental evidences.

Medium entropy FeCoNi nanoalloy supported on reduced graphene oxide for efficient electrochemical detection of roxarsone in food samples.

Herein, a novel FeCoNi(b)-800 ternary metal nanoalloy was uniformly mixed with reduced graphene oxide (RGO) to synthesize the FeCoNi(b)-800@RGO(2:1) composite. The addition of RGO not only stopped the accumulation of FeCoNi(b)-800 alloy, but also heightened the electrocatalytic activity of composite. Particularly, the FeCoNi(b)-800@RGO(2:1) composite displayed the significantly strong electrocatalytic capacity for the reduction of roxarsone (ROX). Furthermore, the FeCoNi(b)-800@RGO(2:1) composite possessed enough porosity and metal catalytic sites, facilitating the transport and electrochemical reduction of the ROX. Thus, the FeCoNi(b)-800@RGO(2:1) composite modified glassy carbon electrode (FeCoNi(b)-800@RGO(2:1)/GCE) showed the superb electrochemical detection effect for ROX with relatively wide working range (0.1-1500 µM) and low detection limit (0.013 µM). Importantly, the FeCoNi(b)-800@RGO(2:1)/GCE sensor could accurately determine the contents of ROX in actual pork, chicken, duck and egg samples, indicating that it had good suitability in food safety monitoring.

Design and fabrication of La-based perovskites incorporated with functionalized carbon nanofibers for the electrochemical detection of roxarsone in water and food samples.

The pentavalent arsenic compound roxarsone (RSN) is used as a feed additive in poultry for rapid growth, eventually ending up in poultry litter. Poultry litter contains chicken manure, which plays a vital role as an affordable fertilizer by providing rich nutrients to agricultural land. Consequently, the extensive use of poultry droppings serves as a conduit for the spread of toxic forms of arsenic in the soil and surface water. RSN can be easily oxidized to release highly carcinogenic As(III) and As(IV) species. Thus, investigations were conducted for the sensitive detection of RSN electrochemically by developing a sensor material based on lanthanum manganese oxide (LMO) and functionalized carbon nanofibers (f-CNFs). The successfully synthesised LMO/f-CNF composite was confirmed by chemical, compositional, and morphological studies. The electrochemical activity of the prepared composite material was examined using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The obtained results confirmed that LMO/f-CNF showed enhanced electrocatalytic activity and improved current response with a good linear range (0.01-0.78 µM and 2.08-497 µM, respectively), exhibiting a low limit of detection (LOD) of 0.004 µM with a high sensitivity of 13.24 µA µM-1 cm-2 towards the detection of RSN. The noteworthy features of LMO/f-CNF composite with its superior electrochemical performance enabled reliable reproducibility, exceptional stability and reliable practical application in the analysis of tap water and food sample, affording a recovery range of 86.1-98.87%.

Biotransformation of roxarsone by earthworms and subsequent risk of soil arsenic release: The role of gut bacteria.

The organoarsenical feed additive roxarsone (ROX) is a ubiquitous threat due to the unpredictable levels of arsenic (As) released by soil bacteria. The earthworms representing soil fauna communities provide hotspots for As biotransformation genes (ABGs). Nonetheless, the role of gut bacteria in this regard is unclear. In this study, the changes in As speciation, bacterial ABGs, and communities were analyzed in a ROX-contaminated soil (50 mg/kg As in ROX form) containing the earthworm Eisenia feotida. (RE vs. R treatment). After 56 d, earthworms reduced the levels of both ROX and total As by 59 % and 17 %, respectively. The available As content was 10 % lower in the RE than in R treatment. Under ROX stress, the total ABG abundance was upregulated in both earthworm gut and soil, with synergistic effects observed following RE treatment. Besides, the enrichment of arsM and arsB genes in earthworm gut suggested that gut bacteria may facilitate As removal by enhancing As methylation and transport function in soil. However, the bacteria carrying ABGs were not associated with the ABG abundance in earthworm gut indicating the unique strategies of earthworm gut bacteria compared with soil bacteria due to different microenvironments. Based on a well-fit structural equation model (P = 0.120), we concluded that gut bacteria indirectly contribute to ROX transformation and As detoxification by modifying soil ABGs. The positive findings of earthworm-induced ROX transformation shed light on the role of As biomonitoring and bioremediation in organoarsenical-contaminated environments.

Roxarsone biotransformation by a nitroreductase and an acetyltransferase in Pseudomonas chlororaphis, a bacterium isolated from soil.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, Rox), a widely used organoarsenical feed additive, can enter soils and be further biotransformed into various arsenic species that pose human health and ecological risks. However, the pathway and molecular mechanism of Rox biotransformation by soil microbes are not well studied. Therefore, in this study, we isolated a Rox-transforming bacterium from manure-fertilized soil and identified it as Pseudomonas chlororaphis through morphological analysis and 16S rRNA gene sequencing. Pseudomonas chlororaphis was able to biotransform Rox to 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA), N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA), arsenate [As(V)], arsenite [As(III)], and dimethylarsenate [DMAs(V)]. The complete genome of Pseudomonas chlororaphis was sequenced. PcmdaB, encoding a nitroreductase, and PcnhoA, encoding an acetyltransferase, were identified in the genome of Pseudomonas chlororaphis. Expression of PcmdaB and PcnhoA in E. coli Rosetta was shown to confer Rox(III) and 3-AHPAA(III) resistance through Rox nitroreduction and 3-AHPAA acetylation, respectively. The PcMdaB and PcNhoA enzymes were further purified and functionally characterized in vitro. The kinetic data of both PcMdaB and PcNhoA were well fit to the Michaelis-Menten equation, and nitroreduction catalyzed by PcMdaB is the rate-limiting step for Rox transformation. Our results provide new insights into the environmental risk assessment and bioremediation of Rox(V)-contaminated soils.

Multifunctional Eu(III)-modified HOFs: roxarsone and aristolochic acid carcinogen monitoring and latent fingerprint identification based on artificial intelligence.

The exploration of multifunctional materials and intelligent technologies used for fluorescence sensing and latent fingerprint (LFP) identification is a research hotspot of material science. In this study, an emerging crystalline luminescent material, Eu3+-functionalized hydrogen-bonded organic framework (Eu@HOF-BTB, Eu@1), is fabricated successfully. Eu@1 can emit purple red fluorescence with a high photoluminescence quantum yield of 36.82%. Combined with artificial intelligence (AI) algorithms including support vector machine, principal component analysis, and hierarchical clustering analysis, Eu@1 as a sensor can concurrently distinguish two carcinogens, roxarsone and aristolochic acid, based on different mechanisms. The sensing process exhibits high selectivity, high efficiency, and excellent anti-interference. Meanwhile, Eu@1 is also an excellent eikonogen for LFP identification with high-resolution and high-contrast. Based on an automatic fingerprint identification system, the simultaneous differentiation of two fingerprint images is achieved. Moreover, a simulation experiment of criminal arrest is conducted. By virtue of the Alexnet-based fingerprint analysis platform of AI, unknown LFPs can be compared with a database to identify the criminal within one second with over 90% recognition accuracy. With AI technology, HOFs are applied for the first time in the LFP identification field, which provides a new material and solution for investigators to track criminal clues and handle cases efficiently.

Interaction between roxarsone, an organic arsenic compound, with humic substances in the soil simulating environmental conditions.

In environmental systems, the soil is a principal route of contamination by various potentially toxic species. Roxarsone (RX) is an arsenic (V) organic compound used to treat parasitic diseases and as an additive for animal fattening. When the animal excretes RX, the residues may lead to environmental contamination. Due to their physicochemical properties, the soil's humic substances (HS) are important in species distribution in the environment and are involved in various specific interaction/adsorption processes. Since RX, an arsenic (V) compound, is considered an emerging contaminant, its interaction with HS was evaluated in simulated environmental conditions. The HS-RX interaction was analyzed by monitoring intrinsic HS fluorescence intensity variations caused by complexation with RX, forming non-fluorescent supramolecular complexes that yielded a binding constant Kb (on the order of 103). The HS-RX interaction occurred through static quenching due to complex formation in the ground state, which was confirmed by spectrophotometry. The process was spontaneous (ΔG < 0), and the predominant interaction forces were van der Waals and hydrogen bonding (ΔH < 0 and ΔS < 0), with an electrostatic component evidenced by the influence of ionic strength in the interaction process. Structural changes in the HS were verified by synchronized and 3D fluorescence, with higher variation in the region referring to the protein-like fraction. In addition, metal ions (except ions Cu(II)) favored HS-RX interaction. When interacting with HS, the RX epitope was suggested by 1H NMR, which indicated that the entire molecule interacts with the superstructure. An enzyme inhibition assay verified the ability to reduce the alkaline phosphatase activity of free and complexed RX (RX-HS). Finally, this work revealed the main parameters associated with HS and RX interaction in simulated environmental conditions, thus, providing data that may help our understanding of the dynamics of organic arsenic-influenced soils.

Bifunctional protein ArsRM contributes to arsenite methylation and resistance in Brevundimonas sp. M20.

BACKGROUND: Arsenic (As) with various chemical forms, including inorganic arsenic and organic arsenic, is the most prevalent water and environmental toxin. This metalloid occurs worldwide and many of its forms, especially arsenite [As(III)], cause various diseases including cancer. Organification of arsenite is an effective way for organisms to cope with arsenic toxicity. Microbial communities are vital contributors to the global arsenic biocycle and represent a promising way to reduce arsenite toxicity. METHODS: Brevundimonas sp. M20 with arsenite and roxarsone resistance was isolated from aquaculture sewage. The arsHRNBC cluster and the metRFHH operon of M20 were identified by sequencing. The gene encoding ArsR/methyltransferase fusion protein, arsRM, was amplified and expressed in Escherichia coli BL21 (DE3), and this strain showed resistance to arsenic in the present of 0.25-6 mM As(III), aresenate, or pentavalent roxarsone. The methylation activity and regulatory action of ArsRM were analyzed using Discovery Studio 2.0, and its functions were confirmed by methyltransferase activity analysis and electrophoretic mobility shift assays. RESULTS: The minimum inhibitory concentration of the roxarsone resistant strain Brevundimonas sp. M20 to arsenite was 4.5 mM. A 3,011-bp arsenite resistance ars cluster arsHRNBC and a 5649-bp methionine biosynthesis met operon were found on the 3.315-Mb chromosome. Functional prediction analyses suggested that ArsRM is a difunctional protein with transcriptional regulation and methyltransferase activities. Expression of ArsRM in E. coli increased its arsenite resistance to 1.5 mM. The arsenite methylation activity of ArsRM and its ability to bind to its own gene promoter were confirmed. The As(III)-binding site (ABS) and S-adenosylmethionine-binding motif are responsible for the difunctional characteristic of ArsRM. CONCLUSIONS: We conclude that ArsRM promotes arsenite methylation and is able to bind to its own promoter region to regulate transcription. This difunctional characteristic directly connects methionine and arsenic metabolism. Our findings contribute important new knowledge about microbial arsenic resistance and detoxification. Future work should further explore how ArsRM regulates the met operon and the ars cluster.

Inhibitory effect of polyethylene microplastics on roxarsone degradation in soils.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, Rox(V)), an extensively used organoarsenical feed additive, enters soils through the application of Rox(V)-containing manure and further degrades to highly toxic arsenicals. Microplastics, as emerging contaminants, are also frequently detected in soils. However, the effects of microplastics on soil Rox(V) degradation are unknown. A microcosm experiment was conducted to investigate soil Rox(V) degradation responses to polyethylene (PE) microplastics and the underlying mechanisms. PE microplastics inhibited soil Rox(V) degradation, with the main products being 3-amino-4-hydroxyphenylarsonic acid [3-AHPAA(V)], N-acetyl-4-hydroxy-m-arsanilic acid [N-AHPAA(V)], arsenate [As(V)], and arsenite [As(III)]. This inhibition was likely driven by the decline in soil pH by PE microplastic addition, which may directly enhance Rox(V) sorption in soils. The decreased soil pH further suppressed the nfnB gene related to nitroreduction of Rox(V) to 3-AHPAA(V) and nhoA gene associated with acetylation of 3-AHPAA(V) to N-AHPAA(V), accompanied by a decrease in the relative abundance of possible Rox(V)-degrading bacteria (e.g., Pseudomonadales), although the diversity, composition, network complexity, and assembly of soil bacterial communities were largely influenced by Rox(V) rather than PE microplastics. Our study emphasizes microplastic-induced inhibition of Rox(V) degradation in soils and the need to consider the role of microplastics in better risk assessment and remediation of Rox(V)-contaminated soils.

Simultaneous oxidation of roxarsone and adsorption of released arsenic by FeS-activated sulfite.

The conventional oxidation-adsorption methods are effective for the removal of roxarsone (ROX) but are limited by complicated operation, toxic residual oxidant and leaching of toxic metal ions. Herein, we proposed a new approach to improve ROX removal, i.e., using the FeS/sulfite system. Experimental results showed that approximately 100% of ROX (20 mg/L) was removed and more than 90% of the released inorganic arsenic (As(V) dominated) was adsorbed on FeS within 40 min. This FeS/sulfite system was a non-homogeneous activation process, and SO4·-, ·OH and 1O2 were identified as reactive oxidizing species with their contributions to ROX degradation being 48.36%, 27.97% and 2.64%, respectively. Based on density functional theory calculations and HPLC-MS results, the degradation of ROX was achieved by C-As breaking, electrophilic addition, hydroxylation and denitrification. It was also found that the released inorganic arsenic was adsorbed through a combination of outer-sphere complexation and surface co-precipitation, and the generated arsenopyrite (FeAsS), a precursor to ecologically secure scorodite (FeAsO4·2H2O), was served as the foundation for further inorganic arsenic mineralization. This is the first attempt to use the FeS/sulfite system for organic heavy metal removal, which proposes a prospective technique for the removal of ROX.

Roxarsone Delivery Nanocomposite Based on Nitrite-Functionalized Mesoporous Polydopamine for Multidrug-Resistant Bacterial Infections via Enhanced Chemo-Photothermal Therapy.

Current treatments for infections caused by multidrug-resistant bacteria still remain challenging and therapeutic materials with high efficacy are of demand. Herein, a bactericidal nanocomposite was constructed by loading Roxarsone (ROX) onto nitrosylated mesoporous polydopamine (named mPDA@NO-ROX). The designed nanocomposite exhibited considerable photothermal effect and controlled NO and ROX co-delivery under the irradiation of near-infrared laser (NIR) to achieve enhanced chemo-photothermal antibacterial therapy. The in vitro antibacterial evaluation of the mPDA@NO-ROX demonstrated the effective elimination of the Gram-negative tetracycline-resistant Escherichia coil and Gram-positive methicillin-resistant Staphylococcus aureus under mild NIR irradiation compared to merely ROX loaded unmodified mPDA, indicating the NO enhanced chemo-photothermal therapy. In addition, the cytotoxicity experiments indicated that mPDA@NO-ROX exhibited only 5 % of hemolysis rate and high cell viability at 1 mg mL-1 against mammalian fibroblasts, suggesting the excellent biocompatibility. In conclusion, the mPDA@NO-ROX could be a promising candidate for anti-infection therapy of multidrug-resistant bacteria.

The role of organic and inorganic substituents of roxarsone determines its binding behavior and mechanisms onto nano-ferrihydrite colloidal particles.

The retention and fate of Roxarsone (ROX) onto typical reactive soil minerals were crucial for evaluating its potential environmental risk. However, the behavior and molecular-level reaction mechanism of ROX and its substituents with iron (hydr)oxides remains unclear. Herein, the binding behavior of ROX on ferrihydrite (Fh) was investigated through batch experiments and in-situ ATR-FTIR techniques. Our results demonstrated that Fh is an effective geo-sorbent for the retention of ROX. The pseudo-second-order kinetic and the Langmuir model successfully described the sorption process. The driving force for the binding of ROX on Fh was ascribed to the chemical adsorption, and the rate-limiting step is simultaneously dominated by intraparticle and film diffusion. Isotherms results revealed that the sorption of ROX onto Fh appeared in uniformly distributed monolayer adsorption sites. The two-dimensional correlation spectroscopy and XPS results implied that the nitro, hydroxyl, and arsenate moiety of ROX molecules have participated in binding ROX onto Fh, signifying that the predominated mechanisms were attributed to the hydrogen bonding and surface complexation. Our results can help to better understand the ROX-mineral interactions at the molecular level and lay the foundation for exploring the degradation, transformation, and remediation technologies of ROX and structural analog pollutants in the environment.

Roxarsone inhibits hepatic stellate cell activation and ameliorates liver fibrosis by blocking TGF-ß1/Smad signaling pathway.

Hepatic fibrosis is a pathological change caused by chronic liver injury and self-repair, and it is the inevitable stage of the development of chronic liver disease to cirrhosis or even liver cancer. Activation of hepatic stellate cells (HSCs) is a core event in the development of liver fibrosis and blockage of the activation of HSCs has been shown to alleviate liver fibrosis. Roxarsone, an organoarsenic additive, with antibiotic effect, growth promotion and improving feed efficiency, is widely used in livestock and animal production. The purpose of this study was to evaluate the therapeutic effect of Roxarsone on liver fibrosis and explore the possible mechanism. We found that Roxarsone could inhibit transforming growth factor-ß1 (TGF-ß1) induced the activation of HSCs and weaken the migration ability. Moreover, Roxarsone administration significantly ameliorated CCl4-induced liver fibrosis in mice with improvement of liver function and decreases of deposition of extracellular matrix (ECM). Mechanism investigations revealed that Roxarsone specifically inhibited the activation of TGF-ß1/Smad signaling pathway, but had no effect on MAPK and PI3K/AKT pathways. These results suggest that Roxarsone has a protective effect on liver fibrosis which provides a new candidate for the treatment of liver fibrosis.

The interfacial behaviors of different arsenic species on polyethylene mulching film microplastics: Roles of the plastic additives.

Plastic additives widely existed in plastic mulching films, but their roles in microplastics (MPs) derived from these plastics as vectors of pollutants were not clear. This work clarified the role of plastic additives on the sorption-desorption behaviors of four arsenic species (arsenite (As(Ⅲ)), arsenate (As(Ⅴ)), roxarsone (ROX), and p-arsanilic acid (p-ASA)) on/from virgin polyethylene (V-PE), white PE mulching film (W-PE, with Si-containing additives), and black PE mulching film (B-PE, with CaCO3 and TiO2 additives) MPs. The maximum sorption amounts of arsenic species on V-PE (3.33-20.10 mg/kg) and W-PE MPs (4.78-21.93 mg/kg) had no significant difference, while those on B-PE (43.02-252.19 mg/kg) facilitated by its additives were up to one order of magnitude greater than V-PE or W-PE (p < 0.05). Desorption hysteresis index (HI) indicated the irreversible arsenic sorption on three PE MPs, especially for B-PE containing additives that can co-precipitate and complex with arsenicals. The effects of pH, humic substances, and coexisting anions on arsenic sorption by B-PE were more obvious than that by V-PE or W-PE MPs, attributing to electrostatic interaction enhanced by CaCO3 and TiO2 additives. This work provides theoretical basis for migration of arsenic species on MPs containing plastic additives and their potential environmental risk assessment.

Highly efficient persulfate catalyst prepared from modified electrolytic manganese residues coupled with biochar for the roxarsone removal.

The contamination of organoarsenic is becoming increasingly prominent while SR-AOPs were confirmed to be valid for their remediation. This study has found that the novel metal/carbon catalyst (Fe/C-Mn) prepared by solid waste with hierarchical pores could simultaneously degrade roxarsone (ROX) and remove As(V). A total of 95.6% of ROX (20 mg/L) could be removed at the concentration of 1.0 g/L of catalyst and 0.4 g/L of oxidant in the Fe/C-Mn/PMS system within 90 min. The scavenging experiment and electrochemical test revealed that both single-electron and two-electron pathways contributed to the ROX decomposition. Spectroscopic analysis suggested the ROX has been successfully mineralized while As(V) was fixed with the surface Fe and Mn. Density functional theory (DFT) calculation and chromatographic analysis indicated that the As7, N8, O9 and O10 sites of ROX molecule were vulnerable to being attacked by nucleophilic, electrophilic and radical, resulting in the formation of several intermediates such as phenolic compounds. Additionally, the low metal leaching concentration during recycling and high anti-interference ability in various water matrices manifested the practicability of Fe/C-Mn/PMS system.

Insights into the influence of Fe(III) on the interaction between roxarsone and humic acid using multi-spectroscopic techniques.

The influence of Fe(III) on the interaction between roxarsone (ROX) and humic acid (HA) was investigated by multi-spectroscopic techniques. The fluorescence quenching experiment indicated that the fluorescence intensity of HA-ROX was quenched by Fe(III) through a static quenching process. Synchronous fluorescence spectra provided further information concerning the competitive combination between ROX and Fe(III) for HA. The results of the dialysis equilibrium experiment confirmed the existence of Fe(III) (0.05-0.1 mmol/L) promotes the combination of HA and ROX. Binding mechanisms were further characterized by FTIR spectroscopy, and the carboxyl functional group is involved in the binding process of HA/Fe/ROX. In addition, acidic and neutral conditions are more conducive to the combination of ROX and HA/Fe than alkaline conditions. The above discussion is of great significance in understanding the environmental fate of ROX under the coexistence of Fe(III) and HA.

Highly Luminescent MOF and Its In Situ Fabricated Sustainable Corn Starch Gel Composite as a Fluoro-Switchable Reversible Sensor Triggered by Antibiotics and Oxo-Anions.

Frequent use of antibiotics and the growth of industry lead to the pollution of several natural resources which is one of the major consequences for fatality to human health. Exploration of smart sensing materials is highly anticipated for ultrasensitive detection of those hazardous organics. The robust porous hydrogen bonded network encompassing a free-NH2 moiety, Zn(II)-based metal-organic framework (MOF) (1), is used for the selective detection of antibiotics and toxic oxo-anions at the ppb level. The framework is able to detect the electronically dissimilar antibiotic sulfadiazine and nitrofurazone via fluorescence "turn-on" and "turn-off" processes, respectively. The antibiotic-triggered reversible fluoro-switching phenomena (fluorescence "on-off-on") are also observed by using the fluorimetric method. An extensive theoretical investigation was performed to establish the fluoro-switching response of 1, triggered by a class of antibiotics and also the sensing of oxo-anions. This investigation reveals that the interchange of the HOMO-LUMO energy levels of fluorophore and analytes is responsible for such a fluoro-switchable sensing activity. Sensor 1 showed the versatile detection ability which is reflected by the detection of a carcinogenic nitro-group-containing drug "roxarsone". In view of the sustainable environment along with quick-responsive merit of 1, an in situ MOF gel composite (1@CS; CS = corn starch) is prepared using 1 and CS due to its useful potential features such as biocompatibility, toxicologically innocuous, good flexibility, and low commercial price. The MOF composite exhibited visual detection of the above analytes as well as antibiotic-triggered reversible fluoro-switchable colorimetric "on-off-on" response. Therefore, 1@CS represents a promising smart sensing material for monitoring of the antibiotics and oxo-anions, particularly appropriate for the real-field analysis of carcinogenic drug molecule "roxarsone" in food specimens.

Fabrication of Praseodymium Vanadate Nanoparticles on Disposable Strip for Rapid and Real-Time Amperometric Sensing of Arsenic Drug Roxarsone.

Nanomaterials have versatile properties owing to their high surface-to-volume ratio and can thus be used in a variety of applications. This work focused on applying a facile hydrothermal strategy to prepare praseodymium vanadate nanoparticles due to the importance of nanoparticles in today's society and the fact that their synthesis might be a challenging endeavor. The structural and morphological characterizations were carried out to confirm the influence of the optimizations on the reaction's outcomes, which revealed praseodymium vanadate (PrVO4) with a tetragonal crystal system. In this regard, the proposed development of electrochemical sensors based on the PrVO4 nanocatalyst for the real-time detection of arsenic drug roxarsone (RXS) is a primary concern. The detection was measured by amperometric (i-t) signals where PrVO4/SPCE, as a new electrochemical sensing medium for RXS detection, increased the sensitivity of the sensor to about ∼2.5 folds compared to the previously reported ones. In the concentration range of 0.001-551.78 µM, the suggested PrVO4/SPCE sensor has a high sensitivity for RXS, with a detection limit of 0.4 nM. Furthermore, the impact of several selected potential interferences, operational stability (2000 s), and reproducibility measurements have no discernible effect on RXS sensing, making it the ideal sensing device feasible for technical analysis. The real-time analysis reveals the excellent efficiency and reliability of the prosed sensor toward RXS detection with favorable recovery ranges between ±97.00-99.66% for chicken, egg, water, and urine samples.