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ENVIRONMENTAL RESEARCH · 2024 · IF 7.7

Underestimated role of hydroxyl radicals for bromate formation in persulfate-based advanced oxidation processes

Wanqi Xu,Congcong Ni,Ning Deng,Xin Huang

In persulfate-based advanced oxidation processes (PS-AOPs), sulfate radicals (SO 4 •- ) have been recognized to play more important roles in inducing bromate (BrO 3 − ) formation rather than hydroxyl radicals (HO • ) because of the stronger oxidation capacity of the former. However, this study reported an opposite result that HO • indeed dominated the formation of bromate instead of SO 4 •- . Quenching experiments were coupled with electron paramagnetic resonance (EPR) detection and chemical probe identification to elucidate the contributions of each radical species. The comparison of different thermal activated persulfates (PDS and PMS) demonstrated that the significant higher bromate formation in HEAT/PMS ([BrO 3 − ]/[Br − ] 0  = 0.8), as compared to HEAT/PDS ([BrO 3 − ]/[Br − ] 0  = 0.2), was attributable to the higher concentration of HO • radicals in HEAT/PMS. Similarly, the bromate formation in UV/PDS ([BrO 3 − ]/[Br − ] 0  = 1.0), with a high concentration of HO • , further underscored the dominant role of HO • . As a result, we quantified that HO • and SO 4 •- radicals accounted 66.7% and 33.3% for bromate formation. This controversial result can be reconciled by considering the critical intermediate, hypobromic acid/hypobromate (HOBr/BrO − ), involved in the transformation of Br − to BrO 3 − . HO • radicals have the chemical preference to induce the formation of HOBr/BrO − intermediates (contributing ∼ 60%) relative to SO 4 •- radicals (contributing ∼ 40%). This study highlighted the dominant role of HO • in the formation of bromate rather than SO 4 •- in PS-AOPs and potentially offered novel insights for reducing disinfection byproduct formation by controlling the radical species in AOPs.

CAS / MDL: 299-11-6
研究领域: 环境科学 · 化学工程
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

A Sequentially activated probe for simultaneous fluorescence imaging of ONOO― and HOBr in brain to indicate Alzheimer’s Disease

Hui Wang,Tiancong Xiu,Xiaoting Zhang,Lianhuan Zhu,Haonan Bi,Ping Li,Bo Tang

Alzheimer's disease (AD) is an irreversible neurodegenerative disorder characterized by progressive cognitive decline and memory loss. However, clinical diagnosis is only effective for patients with obvious clinical symptoms, which cannot provide precise diagnosis in the early stages of AD. Therefore, developing a practical tool for rapid and accurate diagnosis of AD is of paramount importance. Research suggests that reactive oxygen species (ROS), specifically peroxynitrite (ONOO ― ) and hypobromous acid (HOBr), may involve in the progression of AD, which could serve as biomarkers. Research on the simultaneous imaging of two kinds of ROS in AD using a single fluorescence probe remains sparse. To enhance diagnostic accuracy, our research designed an ingenious small-molecule fluorescent probe, NBO, for the sequential detection of ONOO ― and HOBr with distinguishable spectra. By utilization of NBO, elevated ONOO ― and HOBr levels were found in AD brain, and the therapeutic efficacy of AD drugs were successfully assessed.

研究领域: 神经生物学 · 医学影像学 · 生物化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

A novel fluorescent probe for highly selective and sensitive detection of hypobromous acid in arthritis model mice

Xiuzhu Huo,Xia Wang,Ran Yang,Zhaohui Li,Yuanqiang Sun,Lingbo Qu,Huajin Zeng

Hypobromous acid (HOBr), an important active oxygen species in body, plays a critical role in maintaining normal physiology and resisting some diseases. However, due to the extremely low concentration of HOBr in vivo , it is a great challenge to establish an effective analytical method for detection of HOBr. Herein, a novel fluorescent probe for detection of HOBr was synthesized from the reaction between 3-cyanoumbelliferone and hydroxylamine with high yield. The synthesized probe holds great photo-stability and shows real-time response toward HOBr over other reactive oxygen species. The probe has been successfully applied in monitoring HOBr in arthritis model mice and can be used as a real-time monitoring tool for evaluating the development of arthritis in clinic.

CAS / MDL: 19088-73-4 53518-18-6
研究领域: 生物化学 · 医学检测 · 分子生物学
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ACS ES&T Water · 2022 · IF 0

Accelerated Oxidation of Organic Micropollutants during Peracetic Acid Treatment in the Presence of Bromide Ions

Penghui Du,Wen Liu,Zuomin Rao,Junjian Wang

Peracetic acid (PAA), an alternative disinfectant of chlorine, has drawn increasing attention in the application of wastewater treatment. However, little is known about the influence of water matrices on PAA-induced organic micropollutant (OMP) degradation. Here, we found that the coexisting bromide ions (Br–) in water can trigger the oxidation of OMP during PAA treatment but probably result in higher ecotoxicity. Br– can efficiently decompose PAA with a species-specific rate constant (kPAAH/Br–) of 0.198 ± 0.003 M–1·s–1. The thus generated HOBr led to a significant abatement (31.8–81.3%) of OMPs (17α-ethinylestradiol, sulfamethoxazole, naproxen, and phenol) after a 1 h reaction at pH 7.1. The coexisting H2O2 component in the PAA solution can competitively consume HOBr and inhibit OMP transformation. The OMP degradation in the PAA/Br– process was highly pH-dependent and preferred acidic conditions. Furthermore, a comprehensive model was established to simulate the reaction kinetics of the OMP degradation by the PAA/Br– process with good accuracy. High-performance/electrospray ionization-triple quadrupole mass spectrometry results indicated the generation of various brominated products, with higher model-predicted toxicity than their parent compounds. This work significantly advances the understanding of the role of Br– in OMP oxidation by PAA and alerts the possible environmental health risks.

研究领域: 环境科学 · 水处理 · 化学工程 · 毒理学
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Small · 2022 ·Vol. 18 ·期 16 ·2107401 · IF 15.153

Stabilizing Ultrasmall Ceria-Cluster Nanozyme for Antibacterial and Antibiofouling Applications

Qiang Luo,Yunhong Li,Xiaobing Huo,Jinyang Li,Linqian Li,Wei Wang,Yilan Li,Shipeng Chen,Yinqiao Song,Ning Wang

The generation of undesired biofouling in medical and engineering applications results in a reduction in function and durability. Copying functionalities of natural enzymes to combat biofouling by artificial nanomaterials is highly attractive but still challenged by the inferior catalytic activity and specificity principally because of low densities of active sites. Here, an innovate strategy is demonstrated to stabilize high-density ultrasmall ceria clusters on zirconia for biofouling prevention. Benefiting from the unique structure, CeO 2 @ZrO 2 nanozyme can significantly enhance the haloperoxidase-mimicking activity in catalyzing the oxidation of bromide with H 2 O 2 into biocidal hypobromous acid as a result of abundant defects and surface strong acidity sites, inducing impressive antibacterial and antibiofouling capacity compared with that of pristine CeO 2 . This work is expected to open a new avenue for the rational design of cluster catalysts for various targeting catalytic applications.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 催化
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