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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2024 · IF 4.1

Reaction mechanisms of main free radicals (HO•, Cl• and ClO•) with carbamazepine in the UV/Chlorine process

Duanyang Wu,Shengnan Zhang,Jing Xu,Wei Cheng

Carbamazepine (CBZ) is a ubiquitous persistent micropollutant in water. This study evaluated the degradation of CBZ by UV/Chlorine process. The influencing factors, such as chlorine dosage, solution pH, and water matrix constituents (Cl − , HCO 3 – and NOM) on CBZ removal were systematically investigated. The reactive HO•, Cl• and ClO• species were mainly responsible for the degradation of CBZ, and their contributions determined by probes (Benzoic acid, Nitrobenzene and 1,4-Dimethoxybenzene) varied with pH. Theoretical quantum calculations involving a total of 79 transition states suggested that HO• attack CBZ by hydrogen atom transfer (HAT) and radical adduct formation (RAF) mechanisms, while Cl• and ClO• proceed mainly through HAT and RAF mechanism, respectively. The reaction rates between CBZ and free radicals were calculated by evaluating the energy barriers and transition states. Furthermore, the proposed formation pathways and reaction mechanisms of main hydroxylated products and chlorine substituted products were unequivocally authenticated by transition states calculations. Overall, this study combined experimental and computational approaches to provide an in-depth degradation mechanism of CBZ in UV/Chlorine process.

研究领域: 环境科学 · 化学工程
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RSC Advances · 2024 ·Vol. 14 ·期 39 ·28957-28964 · IF 3.9

Mechanism of two styryl BODIPYs as fluorescent probes and protective agents in lipid bilayers against aqueous ClO−

Lu Yang,Yanglin Jiang,Ailin Sun,Mingqing Chen,Qiwei Li,Peng Wang,Jianping Zhang

Two styryl BODIPY derivatives, BOH and BOE, with different hydrophilic properties, were investigated for their reaction mechanisms in lipid bilayers against aqueous ClO−, by both experimental and theoretical methods. Density functional theory (DFT) calculations confirmed their identical conformations in solution. Fluorescence spectra and high-resolution mass spectra corroborated the central vinyl group as a common antioxidation moiety against ClO− oxidation. In giant unilamellar vesicles (GUVs), distinct reaction kinetics with ClO− suggested that BOE provided superior protective effects compared to BOH on lipids. Molecular dynamics simulations indicated that the lipophilic octyloxy group in BOE led to its deeper localization within the lipid phase, bringing it closer to the corresponding lipid target group. This study establishes the two styryl BODIPYs as promising fluorescent probes for detecting aqueous ClO− in lipid-water polyphasic systems.

研究领域: 生物化学 · 分子生物学
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Journal of Energy Chemistry · 2024 · IF 14

Enhancing the stability of NiFe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Yongchao Yao,Shengjun Sun,Hui Zhang,Zixiao Li,Chaoxin Yang,Zhengwei Cai,Xun He,Kai Dong,Yonglan Luo,Yan Wang,Yuchun Ren,Qian Liu,Dongdong Zheng,Weihua Zhuang,Bo Tang,Xuping Sun,Wenchuang (Walter) Hu

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation. Nevertheless, the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry. Herein, we present our recent discovery that the incorporation of Ce into NiFe layered double hydroxide nanosheet array on Ni foam (Ce-NiFe LDH/NF) emerges as a robust electrocatalyst for seawater oxidation. During the seawater oxidation process, CeO 2 is generated, effectively repelling Cl − and inhibiting the formation of ClO − , resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater. The prepared Ce-NiFe LDH/NF requires only overpotential of 390 mV to achieve the current density of 1 A cm −2 , while maintaining long-term stability for 500 h, outperforming the performance of NiFe LDH/NF (430 mV, 150 h) by a significant margin. This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on NiFe LDH in seawater electrolysis for oxygen evolution.

研究领域: 材料科学 · 电化学 · 能源科学
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Journal of Materials Chemistry B · 2017 ·Vol. 5 ·期 29 ·5854-5861 · IF 4.543

Near-infrared BODIPY-based two-photon ClO− probe based on thiosemicarbazide desulfurization reaction: naked-eye detection and mitochondrial imaging

Bao-xing Shen,Ying Qian,Zheng-qing Qi,Chang-gui Lu,Qi Sun,Xiang Xia,Yi-ping Cui

Hypochlorite serves as a significant antimicrobial agent in the human immune system, and its detection is of great importance. Herein, a novel near-infrared BODIPY-based ClO− fluorescent probe (NCS-BOD-OCH3) was designed and synthesized. The emission bands of NCS-BOD-OCH3 concentrated at 595 nm and 665 nm. Since the electron withdrawing group 1,3,4-oxadiazole was formed after the desulfurization reaction, the fluorescence intensity of NCS-BOD-OCH3 decreased significantly in THF/H2O (v/v, 1 : 1, buffered with 10 mM PBS pH = 7.4), which is visible to the naked eye with an obvious color change. NCS-BOD-OCH3 can realize the two-photon up-converted fluorescence emission. The low detection limit was calculated from the titration results, with the figure for NCS-BOD-OCH3/ClO− being 1.15 × 10−6 M. The result of living cell imaging experiment demonstrated that NCS-BOD-OCH3 can successfully detect ClO− in living cells and can serve as a NIR mitochondrial imaging agent. It is an excellent platform for developing NIR ClO− fluorescent probes.

研究领域: 生物化学 · 医学影像学 · 化学生物学
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ENVIRONMENTAL RESEARCH · 2025 · IF 7.7

A cellulose-based near-infrared fluorescent probe for ratiometric imaging and visual monitoring of ClO− in water via smartphone

Wei Bi,Chuanli Ren,Yuxin Xiao,Feng Wang,Qingmao Long,Yanfei Lin,Xinjie Yang,Li Liu,Lianpeng Zhang,Guanben Du

Cellulose is the most abundant renewable biomass resource on Earth, with good biodegradability and biocompatibility. In this study, a novel cellulose-based near-infrared fluorescent probe MN@NIR for ClO − detection was developed by amination modification of microcrystalline cellulose (MCC), followed by the introduction of naphthalimide fluorophores and dicyanoisophorone groups. The probe MN@NIR exhibits excellent fluorescence properties with dual-emission peaks at 543 nm and 690 nm, the latter falling within the near-infrared (NIR) window. It shows highly specific “ratiometric” and “colorimetric” fluorescence responses to ClO − , with the fluorescence color gradually changing from red to blue as the ClO − concentration increases. Notably, the probe demonstrates a rapid response time (2 min) and excellent selectivity and anti-interference properties. The fluorescence film prepared from the probe shows outstanding specificity for ClO − and has been successfully applied to the visual monitoring of ClO − in water samples. Furthermore, this study combines smartphone image analysis technology to develop a G/B color ratio- ClO − monitoring platform, providing a new solution for the quantitative analysis of ClO − concentrations in water and on-site rapid detection.

CAS / MDL: 9005-38-3
研究领域: 分析化学 · 材料科学 · 环境监测 · 生物成像 · 传感器与检测技术
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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

Assessing ClO- level during ER stress and cellular senescence through a ratio fluorescent probe with dual organelle targeting ability

Yi-Min Shan,Kang-Kang Yu,Nan Wang,Fan-Yuan Yu,Kun Li,Yan-Hong Liu,Xiao-Qi Yu

More evidence supports that endoplasmic reticulums stress (ER stress) has close relationship with many disease, including Alzheimer’s disease, and such diseases are often closely related to senescence. Both ER stress and senescence involve disorder of redox regulation and may further cause ClO - accumulation. It is of great importance to develop a tool to visualize ralated organelles to investigate the role of ClO - during ER stress or senescence. In this work, a novel dual-targetable ClO - probe RT-ER was designed, and the probe could image endoplasmic reticulums and lysosome by sequence under stimulation of ClO - . RT-ER worked in a ratiometric manner and was extremely sensitive to ClO - ( ~ 484 folds enchancement within 10 s after the stimulation of ClO - ). RT-ER showed great biocompatibility and was further applied in living cells imaging. We demonstrated that RT-ER enables both exogenous and endogenous ClO - imaging. Compared with the commercial dye Lysosome-Tracker Deep Red, RT-ER showed better photobleaching resistance. We successfully used RT-ER to track the interaction between endoplasmic reticulum and lysosome after ClO - accumulation. More importantly, with the help of RT-ER, we further revealed the level of ClO - change during ER stress and senescence, which will facilitate the functional study of ClO - −disease contacts.

研究领域: 生物化学 · 分子生物学 · 细胞生物学 · 疾病机制
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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

Insight into the performance of UV/chlorine/TiO2 on carbamazepine degradation: The crucial role of chlorine oxide radical (ClO•)

Haochen Zhang,Zhuoyu Li,Xiaoqun Zhou,Xiaohui Lu,Haiteng Gu,Jun Ma

The UV/chlorine (UC) system is a homogeneous advanced oxidation process with increasing attention in water decontamination . The addition of TiO 2 is a newly found strategy to enhance the generation of hydroxyl radical (HO • ) and chlorine radical (Cl • ) in the UC system. However, the crucial role of chlorine oxide radical (ClO • , generated by the reactions of HO • and Cl • with chlorine) on pollutant degradation , has not been noticed in UV/chlorine/TiO 2 (UCT), the heterogeneous photocatalytic system for chlorine activation. Herein, the role of ClO • in UCT was clarified through quenching experiments combined with model simulations during carbamazepine degradation. Tert -butyl alcohol completely inhibited while bicarbonate only partly suppressed carbamazepine degradation in UCT, indicating the important role of ClO • . The second-order reaction rate constant between ClO • and carbamazepine ( k ClO•,carbamazepine ) was fitted to be (1.21 ± 0.08) × 10 7 M −1 s −1 by the kinetic model, which avoided the influence of carbonate radical (CO 3 •− ), whose contribution couldn't be excluded during k ClO•,carbamazepine determination in commonly used competitive kinetic methods with bicarbonate. With the obtained k ClO•,carbamazepine , model simulation suggested that ClO • contributed about 50 % to carbamazepine degradation in UCT, and its concentration was less affected under varied conditions (solution pH, chlorine, bicarbonate, and chloride concentration) to keep an efficient carbamazepine degradation. On the contrary, pollutant degradation dominated by HO • in UCT was largely inhibited with the increase of pH, chlorine, and bicarbonate concentration. In addition to the promotion of degradation efficiency, less disinfection byproducts and lower energy requirement were found in UCT compared with UC. Furthermore, UCT could maintain satisfactory degradation efficiency and energy saving in ground water and surface water samples. Results of this study unraveled the crucial role of ClO • for pollutant degradation in UCT, and showed bright prospects and great potentials of the system in water treatment .

CAS / MDL: 7681-52-9
研究领域: 环境科学 · 化学工程
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Dye-based dual-emission Eu-MOF synthesized by Post-modification for the sensitive ratio fluorescence visualization sensing of ClO-

Jie Xiong,Yunfang Xiao,Jiaman Liang,Jian Sun,Lixia Gao,Qiuju Zhou,Dan Hong,Kejun Tan

As we all know, excessive hypochlorite will be transformed into highly toxic substances, while insufficient hypochlorite can not completely kill bacteria and viruses in water. Therefore, it is desirable to develop a new analytical method to detect ClO - in environmental water. Here, a novel and simple fluorescence sensor was constructed for monitoring ClO - by an effective strategy. An Acriflavine@lanthanide metal-organic framework (Acr@Eu(BTEC)) was designed by covalently integrating amino-rich dye (Acr) and carboxyl-rich Eu(BTEC) via post-synthesis method. The created fluorescence sensor has two emission centers originating from Acr and Eu(BTEC), respectively. In the presence of ClO - , the strong green fluorescence derived from Acr was significantly quenched, while the invariant red emission from Eu 3+ acted as the reference signal. Thus, Acr@Eu(BTEC) with two emissions was developed as a ratiometric fluorescence sensor for highly sensitive and selective detection of ClO - . The limit of detection (LOD) was as low as 10.75 nM. Moreover, visual detection of ClO - by the naked eyes is feasible with obvious fluorescent color changes from green to orange and then red. This method shows excellent performance in practical application, which suggests that it has great potential in water quality monitoring.

研究领域: 环境科学 · 分析化学
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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2026 · IF 4.4

A ratiometric nopinyl-derived fluorescent probe for detecting hypochlorite (ClO−) with high sensitivity and its application in living biological systems

Mingxin Li,Lei Zhou,Hao Huang,Xueyuan Wang,Xiaomeng Kang,Dangqin Jin,Irfan Purnawan,Nurul Hidayati Fithriyah,Qin Xu,Shifa Wang

A ratiometric fluorescent probe was synthesized for detecting hypochlorite based on nopinone. • The optical properties and detection performances of the probe were studied comprehensively. • The nopinyl-based chemosensor exhibits excellent capability and was applied in bioimaging. Hypochlorous acid (HOCl)/hypochlorite (ClO − ), an endogenous reactive oxygen species (ROS), plays a major part in physiological and pathological processes. The nopinone derivatives have been proved to be a good fluorophore scaffold and applied for the detection of multiple analytes, which benefited from its natural product properties, good biocompatibility, modifiability, and good photochemical properties. Herein, a ratiometric fluorescent probe ( NPBM ) for detecting ClO − was designed, which exhibited a remarkable fluorescence change from yellow to cyan in response to ClO − . The probe could quantitatively determine the concentrations of ClO − with excellent selectivity, fast response time, as well as low limit of detection (0.266 μM). High resolution mass spectral analysis demonstrated that ClO − triggered the oxidative cleavage of the bridge double bond in NPBM , resulting in significant change in fluorescence. In particular, benefiting from favorable biocompatibility and efficient cell-membrane permeability, NPBM has been successfully applied for ratiometric fluorescence imaging of exogenous ClO − in living HeLa human cervical cancer cells and zebrafish models. Such superior comprehensive performance endows NPBM with promising prospects for ClO − detection in complex biological systems. Therefore, NPBM has a potential application for the development of tools for detecting ClO − .

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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Ratiometric colorimetric and fluorometric dual-sensing system based on anthracene derivatives for the determination of ClO− and total antioxidant capacity

Yan Zhang,Binling Yan,Bing Liu,Yuting Wang,Wenjing Qi,Lianzhe Hu,Jiaxing Song

In this work, a fluorescent small molecule based on 9,10-distyryl anthracene (DSA-2OH) with AIE properties was prepared. DSA-2OH can be oxidized by hypochlorite (ClO − ) to oxidized DSA (ODSA), which can be re-reduced to DSA-2OH by reducing agents. This oxidation–reduction process is accompanied by changes in fluorescence intensity and absorption wavelength. Based on this principle, a colorimetric/fluorometric dual-mode assay for the determination of ClO − and the total antioxidant capacity (TAC) are realized. In contrast to the colorimetric method, the fluorometric method has better detection effect. The fluorometric detection method can detect ClO − and ascorbic acid (AA) in a three-order-of-magnitude concentration range (0.1–20 μM and 0.2–30 μM). The detection limits (LOD) of fluorometric methods for ClO − and AA are 44 nM and 55 nM, respectively. The two methods can mutually validate each other to improve detection accuracy. The proposed assay can detect TAC in drinks such as orange juice, kiwi juice and drinking water with recoveries ranging from 95 % to 105 %, which can help us to make healthier and more sensible dietary choices.

研究领域: 分析化学 · 生物医学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

A super large Stokes shift ratiometric fluorescent probe for highly selective sensing of ClO− in bio-imaging and real water samples

Cheng-lu Zhang,Xiang-ling Li,Yan-hua Jiang,Yi-ning Zhang,Yan-xuan Xie,Yue-dong Sun,Cui Liu

Based on the fluorescence resonance energy transfer (FRET), a ratiometric fluorescent probe ( NQ ) was successfully designed and synthesized, in which quinolinone moiety was selected as the energy donor and naphthalimide block as the energy acceptor. NQ has a super large Stokes shift (231 nm) and a big quantum yield (0.463). Compared with previously reported probes with similar recognition sites, NQ can high sensitively and selectively recognize ClO − with a much low limit of detection (LOD = 21 nM) and extremely rapid response time (20 s). NQ has a strong anti-interference effect and a color change in the solution which can be seen by the “naked eye”. Moreover, NQ can be applied to detect ClO − in real water samples and living cells imaging.

研究领域: 分析化学 · 生物医学 · 环境科学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 8 ·1561-1568 · IF 3.286

Highly sensitive and selective “off-on” fluorescent sensing platform for ClO− in water based on silicon quantum dots coupled with nanosilver

Liu Lirong,Zhu Gangbing,Zeng Wei,Lv Baohe,Yi Yinhui

We present a new “off-on” fluorescence probe for detecting hypochlorite (ClO − ) based on silicon quantum dots coupled with silver nanoparticles (SiQDs/AgNPs) as nanocomplexes. Via introducing N -[3-(trimethoxysilyl)propyl]ethylenediamine and catechol as initial reactants, silicon quantum dots (SiQDs) with excellent properties were synthesized through a simple hydrothermal method. Transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the morphology and structure of quantum dots. The fluorescence of SiQDs could be quenched by the silver nanoparticles (AgNPs) by surface plasmon-enhanced energy transfer (SPEET) from SiQDs (donor) to AgNPs (acceptor). The AgNPs could be etched by adding ClO − , thus freeing the SiQDs from the AgNP surfaces and restoring the SiQDs’ fluorescence. The sensing system exhibits many advantages, such as wide linear response range, high sensitivity, and excellent selectivity. Under optimized conditions, wide linear ranges (from 0.1 to 100.0 μM) and low detection limits (0.08 μM) were obtained for ClO − . Graphical Abstract

研究领域: 分析化学 · 环境科学
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