-
Environmental Science and Pollution... Jan 2022Iron species that occur in natural surface water could affect the photochemical behavior of pollutants. Complexation between iron species and polycarboxylate or heavy...
Iron species that occur in natural surface water could affect the photochemical behavior of pollutants. Complexation between iron species and polycarboxylate or heavy metals has been widely reported, where the ligands could be oxidized via ligand-to-metal charge transfer (LMCT) by light inducement. Such complexation and photochemical reactions might also occur for low valance metal-containing organic compounds, which is worthy of investigation. This work studied the phototransformation of p-arsanilic acid (ASA), an organic arsenic compound that is widely used as a feed additive in the poultry industry, by colloidal ferric hydroxide (CFH) using black light lamps (λ = 365 nm) as the light source. The results revealed the contribution to ASA transformation at circumneutral conditions by CFH through an LMCT process, which is the same as that for As(III). The complexation between ASA and CFH was investigated using UV-vis spectroscopy. The estimated equilibrium constant for the CFH-ASA complex was log K = 4.22. The analysis of the photoproducts found the generation of both inorganic and organic arsenic. Our findings confirmed the similarities in the photochemical mechanisms of ASA and As(III) in the presence of CFH. The results help in further understanding the fate of organoarsenicals in the surface water environment.
Topics: Arsanilic Acid; Colloids; Ferric Compounds; Ultraviolet Rays; Water
PubMed: 34415520
DOI: 10.1007/s11356-021-15975-z -
Frontiers in Neurology 2023Betahistine is widely used for the treatment of various vestibular disorders. However, the approved oral administration route and maximum daily dose are evidently not...
INTRODUCTION
Betahistine is widely used for the treatment of various vestibular disorders. However, the approved oral administration route and maximum daily dose are evidently not effective in clinical trials, possibly due to a major first-pass metabolism by monoamine oxidases (MAOs). The current study aimed to test different application routes (i.v./s.c./p.o.), doses, and concurrent medication (with the MAO-B inhibitor selegiline) for their effects on behavioral recovery and cerebral target engagement following unilateral labyrinthectomy (UL) in rats.
METHODS
Sixty rats were subjected to UL by transtympanic injection of bupivacaine/arsanilic acid and assigned to five treatment groups: i.v. low-dose betahistine (1 mg/kg bid), i.v. high-dose betahistine (10 mg/kg bid), p.o. betahistine (1 mg/kg bid)/selegiline (1 mg/kg once daily), s.c. betahistine (continuous release of 4.8 mg/day), and i.v. normal saline bid (sham treatment; days 1-3 post-UL), respectively. Behavioral testing of postural asymmetry, nystagmus, and mobility in an open field was performed seven times until day 30 post-UL and paralleled by sequential cerebral [F]-FDG-μPET measurements.
RESULTS
The therapeutic effects of betahistine after UL differed in extent and time course and were dependent on the dose, application route, and selegiline co-medication: Postural asymmetry was significantly reduced on 2-3 days post-UL by i.v. high-dose and s.c. betahistine only. No changes were observed in the intensity of nystagmus across groups. When compared to sham treatment, movement distance in the open field increased up to 5-fold from 2 to 30 days post-UL in the s.c., i.v. high-dose, and p.o. betahistine/selegiline groups. [F]-FDG-μPET showed a dose-dependent rCGM increase in the ipsilesional vestibular nucleus until day 3 post-UL for i.v. high- vs. low-dose betahistine and sham treatment, as well as for p.o. betahistine/selegiline and s.c. betahistine vs. sham treatment. From 1 to 30 days post-UL, rCGM increased in the thalamus bilaterally for i.v. high-dose betahistine, s.c. betahistine, and p.o. betahistine/selegiline vs. saline treatment.
DISCUSSION
Betahistine has the potential to augment the recovery of dynamic deficits after UL if the administration protocol is optimized toward higher effective plasma levels. This may be achieved by higher doses, inhibition of MAO-based metabolism, or a parenteral route. imaging suggests a drug-target engagement in central vestibular networks.
PubMed: 37538257
DOI: 10.3389/fneur.2023.1175481 -
ACS Applied Materials & Interfaces Oct 2023Metal-organic frameworks (MOFs) are emerging as advanced nanoporous materials to remove phenylarsenic acid, -arsanilic acid (-ASA), and roxarsone (ROX) in the aqueous...
Metal-organic frameworks (MOFs) are emerging as advanced nanoporous materials to remove phenylarsenic acid, -arsanilic acid (-ASA), and roxarsone (ROX) in the aqueous solution, while MOFs are often present as powder state and encounter difficulties in recovery after adsorption, which greatly limit their practical application in the aqueous environments. Herein, MIL-101 (Fe), a typical MOF, was mixed with sodium alginate and gelatin to prepare MIL-101@CAGE by three-dimensional (3D) printing technology, which was then used as a separatable adsorbent to remove phenylarsenic acid in the aqueous solution. The structure of 3D-printed MIL-101@CAGE was first characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetry and differential thermogravimetry (TG-DTG). The octahedral morphology of MIL-101 (Fe) was found unchanged during the 3D printing process. Then, the adsorption process of MIL-101@CAGE on phenylarsenic acids was systematically investigated by adsorption kinetics, adsorption isotherms, adsorption thermodynamics, condition experiments, and cyclic regeneration experiments. Finally, the adsorption mechanism between MIL-101@CAGE and phenylarsenic acid was further investigated. The results showed that the Langmuir, Freundlich, and Temkin isotherms were well fit, and according to the Langmuir fitting results, the maximum adsorption amounts of MIL-101@CAGE on -ASA and ROX at 25 °C were 106.98 and 120.28 mg/g, respectively. The removal of -ASA and ROX by MIL-101@CAGE remained stable over a wide pH range and in the presence of various coexisting ions. The regeneration experiments showed that the 3D-printed MIL-101@CAGE could still maintain a more than 90% removal rate after five cycles. The adsorption mechanism of this system might include π-π stacking interactions between the benzene ring on the phenylarsenic acids and the organic ligands in MIL-101@CAGE, hydrogen-bonding, and ligand-bonding interactions (Fe-O-As). This study provides a new idea for the scale preparation of a separatable and recyclable adsorbent based on MOF material for the efficient removal of phenylarsenic acid in the aqueous solution.
PubMed: 37816194
DOI: 10.1021/acsami.3c10766 -
Chemosphere Dec 2020Organic arsenicals are important environment pollutants due to wide use in livestock and toxicity of degradation products. In this work we report about the efficient...
Organic arsenicals are important environment pollutants due to wide use in livestock and toxicity of degradation products. In this work we report about the efficient photodegradation of the p-arsanilic acid (p-ASA) and its decomposition products in the Fe(III)-oxalate assisted approach under nature-relevant conditions. At neutral pH under near-visible UV irradiation the Fe(III) oxalate complexes generate the primary oxidizing intermediate, OH radical (the quantum yield of ϕ ∼ 0.06), which rapidly reacts with p-ASA with high rate constant, (8.6 ± 0.5) × 10 Ms. Subsequent radical reactions result in the complete photooxidation of both p-ASA and basic aromatic photoproducts with the predominant formation of inorganic arsenic species, mainly As(V), under optimal conditions. Comparing with the direct UV photolysis, the presented Fe(III)-oxalate mediated degradation of p-ASA has several advantages: higher efficiency at low p-ASA concentration and complete degradation of organic arsenic by-products without use of short-wavelength UV radiation. The obtained results illustrate that the Fe(III)-oxalate complexes are promising natural photosensitizers for the removal of arsenic pollutants from contaminated waters.
Topics: Arsanilic Acid; Arsenic; Ferric Compounds; Hydrogen-Ion Concentration; Iron; Organic Chemicals; Oxalates; Photolysis; Ultraviolet Rays
PubMed: 32731031
DOI: 10.1016/j.chemosphere.2020.127770 -
Applied and Environmental Microbiology Jan 2020The organoarsenical feed additive 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone [ROX]) is widely used and released into the environment. We previously showed a...
-Hydroxyarylamine -Acetyltransferases Catalyze Acetylation of 3-Amino-4-Hydroxyphenylarsonic Acid in the 4-Hydroxy-3-Nitrobenzenearsonic Acid Transformation Pathway of sp. Strain CZ-1.
The organoarsenical feed additive 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone [ROX]) is widely used and released into the environment. We previously showed a two-step pathway of ROX transformation by sp. strain CZ-1 involving the reduction of ROX to 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) and the acetylation of 3-AHPAA to -acetyl-4-hydroxy--arsanilic acid (N-AHPAA) (K. Huang, H. Peng, F. Gao, Q. Liu, et al., Environ Pollut 247:482-487, 2019, https://doi.org/10.1016/j.envpol.2019.01.076). In this study, we identified two genes ( and ), encoding -hydroxyarylamine -acetyltransferases, as responsible for 3-AHPAA acetylation in sp. strain CZ-1. The results of genetic disruption and complementation showed that both genes are involved in ROX biotransformation and that is the major 3-AHPAA acetyltransferase gene. Quantitative reverse transcription-PCR analysis showed that the relative expression level of was 3-fold higher than that of Each of the recombinant NhoAs was overexpressed in BL21 and homogenously purified as a dimer by affinity chromatography. Both purified NhoAs catalyzed acetyl coenzyme A-dependent 3-AHPAA acetylation. The values of 3-AHPAA for NhoA1 and NhoA2 were 151.5 and 428.3 μM, respectively. Site-directed mutagenesis experiments indicated that two conserved arginine and cysteine residues of each NhoA were necessary for their enzyme activities. Roxarsone (ROX) is an organoarsenic feed additive that has been widely used in poultry industries for growth promotion, coccidiosis control, and meat pigmentation improvement for more than 70 years. Most ROX is excreted in the litter and dispersed into the environment, where it is transformed by microbes into different arsenic-containing compounds. A major product of ROX transformation is -acetyl-4-hydroxy--arsanilic acid (N-AHPAA), which is also used as a clinical drug for treating refractory bacterial vaginosis. Here, we report the cloning and functional characterization of two genes encoding -hydroxyarylamine -acetyltransferases, NhoA1 and NhoA2, in sp. strain CZ-1, which catalyze the acetylation of 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) formed by the reduction of ROX to N-AHPAA. This study provides new insights into the function of -hydroxyarylamine -acetyltransferase in the transformation of an important organoarsenic compound.
Topics: Acetylation; Acetyltransferases; Arsenicals; Bacterial Proteins; Enterobacter; Metabolic Networks and Pathways
PubMed: 31676473
DOI: 10.1128/AEM.02050-19 -
Journal of Colloid and Interface Science May 2020Aromatic organoarsenicals are heavily used as poultry feed additives, and the application of manure containing these compounds could release toxic inorganic arsenic into...
HYPOTHESIS
Aromatic organoarsenicals are heavily used as poultry feed additives, and the application of manure containing these compounds could release toxic inorganic arsenic into the environment. Bimetal ferrites are recognized as promising sorbents in removal of organoarsenicals with formation of FeOAs complexes, and their high saturation magnetization also allows easy sorbent separation.
EXPERIMENTS
Herein, a flower-like CoFeO sorbent was synthesized through an environmental-friendly process.
FINDINGS
The flower-like CoFeO particles have abundant mesopores and a large specific surface area of 48.4 m/g. At an equilibrium concentration of 80 μmol/L, the sorption capacities towards p-arsanilic acid (p-ASA), roxarsone (ROX), 4-hydroxyphenylarsonic acid (4-HPAA), 2-aminophenylarsonic acid (2-APAA), phenylarsonic acid (PAA), and 2-nitrophenylarsonic acid (2-NPAA) were 38.1, 45.7, 38.7, 39.3, 33.0, and 32.8 mg/g, respectively. Langmuir model and pseudo-second-order kinetics could well fit the sorption isotherms and rates. The sorption performance was better under acidic conditions due to enhanced electrostatic attraction. Humic acid (HA) and PO inhibited the sorption through competing for sorption sites, while Fe promoted sorption due to formation of additional FeOAs complexes on sorbent surface. The experimental observations, spectroscopic insights, and density functional theory (DFT) calculations consistently indicate that the sorption of aromatic organoarsenicals on the flower-like CoFeO particles occurs mainly through formation of inner-sphere complexes. The flower-like CoFeO could be regenerated and reused over multiple cycles. The high sorption capacities, together with its magnetic property, make the flower-like CoFeO an attractive sorbent for removing aromatic organoarsenicals from wastewater.
PubMed: 32087406
DOI: 10.1016/j.jcis.2020.02.004 -
Biomedicines Aug 2022Damage to the peripheral vestibular system is known to generate a syndrome characterized by postural, locomotor, oculomotor, perceptual and cognitive deficits. Current...
Damage to the peripheral vestibular system is known to generate a syndrome characterized by postural, locomotor, oculomotor, perceptual and cognitive deficits. Current pharmacological therapeutic solutions for these pathologies lack specificity and efficacy. Recently, we demonstrated that apamin, a specific SK channel blocker, significantly reduced posturo-locomotor and oculomotor deficits in the cat and the rat. The aim of the present study was to test the antivertigo potential of compounds belonging to the SK antagonists family, such as Acacetin and Fluoxetine. Young rats were subjected to unilateral ototoxic lesions of the vestibular organ using transtympanic administration of arsanilic acid (TTA) to evoke unilateral vestibular loss (UVL). Vestibular syndrome was monitored using behavioural evaluation allowing appreciation of the evolution of static and dynamic posturo-locomotor deficits. A significant effect of the TTA insult was only found on the distance moved, the mean body velocity and the not moving time. From day 2 to week 2 after TTA, the distance moved and the mean body velocity were significantly decreased, while the not moving time was significantly increased. Acacetin does not evoke any significant change in the vestibular posturo-locomotor parameters' kinetics. Administration of Fluoxetine two weeks before TTA and over three weeks after TTA (preventive group) does not evoke any significant change in the vestibular posturo-locomotor parameters' kinetics. Administration of Fluoxetine from three weeks after TTA significantly delayed the functional recovery. This study demonstrates that Acacetin or Fluoxetine in TTA vestibulo-injured rats does not bring any significant benefit on the posture and locomotor balance deficits.
PubMed: 36140199
DOI: 10.3390/biomedicines10092097 -
Journal of Hazardous Materials Jan 2023Plastic additives widely existed in plastic mulching films, but their roles in microplastics (MPs) derived from these plastics as vectors of pollutants were not clear....
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 CaCO and TiO 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 CaCO and TiO additives. This work provides theoretical basis for migration of arsenic species on MPs containing plastic additives and their potential environmental risk assessment.
Topics: Microplastics; Plastics; Arsenic; Arsenates; Polyethylene; Arsenites; Roxarsone; Humic Substances; Arsanilic Acid; Adsorption; Arsenicals; Environmental Pollutants; Water Pollutants, Chemical
PubMed: 36179620
DOI: 10.1016/j.jhazmat.2022.130037 -
Food Chemistry Apr 2021This study investigated the effect of seaweed supplementation (Ulva lactuca (UL) or Sargassum hemiphyllum var. chinense (SHC)) on the distribution and metabolites of As...
This study investigated the effect of seaweed supplementation (Ulva lactuca (UL) or Sargassum hemiphyllum var. chinense (SHC)) on the distribution and metabolites of As in broiler breasts. Broilers fed 5% UL or 5% SHC ingested 1.4- or 78- fold greater total As than birds fed the control diet. The majority of As species were arsenate in the SHC feed and dimethylarsinic acid in breasts from chicks fed the SHC-containing diet. Arsenate and arsenobetaine were the dominant metabolites in the UL-containing feed, and arsenobetaine was the major metabolite in breasts from chicks fed the UL-containing diet. Feeding SHC enhanced hepatic S-adenosyl-methionine and arsenic methyltransferase, whereas feeding UL elevated renal arsenic methyltransferase. Taken together, considerable variation in the profiles of As species and As metabolites existed in broilers fed seaweed. The use of SHC-containing feeds in poultry production should be approached cautiously because of the potential accumulation of inorganic As species in chicken breasts.
Topics: Animals; Arsenic; Chickens; Diet; Sargassum; Ulva; Vegetables
PubMed: 33077282
DOI: 10.1016/j.foodchem.2020.128346 -
Chemosphere Dec 2022Organoarsenical antibiotics pose a severe threat to the environment and human health. In aquatic environment, dissolved organic matter (DOM)-mediated photochemical...
Organoarsenical antibiotics pose a severe threat to the environment and human health. In aquatic environment, dissolved organic matter (DOM)-mediated photochemical transformation is one of the main processes in the fate of organoarsenics. Dicarbonyl is a typical redox-active moiety in DOM. However, the knowledge on the photoconversion of organoarsenics by DOM, especially the contributions of dicarbonyl moieties is still limited. Here, we systematically investigated the photochemical transformation of three organoarsenics with the simplest β-diketone, acetylacetone (AcAc), as a model dicarbonyl moiety of DOM. The presence of AcAc significantly enhanced the photochemical conversion of roxarsone (ROX), whereas only minor effects were observed for 3-amino-4-hydroxyphenylarsonic acid (HAPA) and arsanilic acid (ASA), because the latter two (with an amino (-NH) group) are more photoactive than ROX (with a nitro (-NO) group). The results demonstrate that AcAc was a potent photo-activator and the reduction of -NO to -NH might be a rate-limiting step in the phototransformation of ROX. At a 1:1 M ratio of AcAc to ROX, the photochemical transformation rate of ROX was increased by 7 folds. In O-rich environment, singlet oxygen, peroxide radicals, and ·OH were the main reactive species that led to the breakage of the C-As bond in ROX and the oxidation of the released arsono group to arsenate, whereas the triplet-excited state of AcAc (AcAc*) and carbon-centered radicals from the photolysis of AcAc dominated in the reductive transformation of ROX. In anoxic environment, 3-amino-4-hydroxyphenylarsonic acid was one of the main reductive transformation intermediates of ROX, whose photolysis rate was about 35 times that of ROX. The knowledge obtained here is of great significance to better understand the fate of organoarsenics in natural environment.
Topics: Anti-Bacterial Agents; Arsanilic Acid; Arsenates; Carbon; Humans; Nitrogen Dioxide; Oxidation-Reduction; Pentanones; Peroxides; Photolysis; Roxarsone; Singlet Oxygen; Water Pollutants, Chemical
PubMed: 36084835
DOI: 10.1016/j.chemosphere.2022.136326