MOLECULES
·
2020
·Vol. 25
·期 12
·2725
·
IF 3.267
Xuefei Zhou,Haowei Wu,Longlong Zhang,Bowen Liang,Xiaoqi Sun,Jiabin Chen
Advanced oxidation processes (AOPs) are effective ways to degrade refractory organic contaminants, relying on the generation of inorganic radicals (e.g.,•OH and SO4•−). Herein, a novel AOP with organic radicals (R-O•) was reported to degrade contaminants. Lanthanum cobaltite perovskite (LaCoO3) was used to activate peracetic acid (PAA) for organic radical generation to degrade sulfamethoxazole (SMX). The results show that LaCoO3exhibited an excellent performance on PAA activation and SMX degradation at neutral pH, with low cobalt leaching. Meanwhile, LaCoO3also showed an excellent reusability during PAA activation. In-depth investigation confirmed CH3C(O)O•and CH3C(O)OO•as the key reactive species for SMX degradation in LaCoO3/PAA system. The presence of Cl−(1–100 mM) slightly inhibited the degradation of SMX in the LaCoO3/PAA system, whereas the addition of HCO3−(0.1–1 mM) and humic aid (1–10 mg/L) could significantly inhibit SMX degradation. This work highlights the generation of organic radicals via the heterogeneous activation of PAA and thus provides a promising way to destruct contaminants in wastewater treatment.Keywords:advanced oxidation processes (AOPs);peracetic acid;LaCoO3;organic radicals
研究领域:
环境科学
·
化学工程
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DOI
PubMed
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 19
·6385
·
IF 4.927
Chengzhi Yu,Libin Zheng,Yongyuan Hong,Jiabin Chen,Feng Gao,Yalei Zhang,Xuefei Zhou,Libin Yang
Advanced oxidation processes (AOPs) demonstrate great micropollutant degradation efficiency. In this study, CuFe2O4was successfully used to activate peracetic acid (PAA) to remove Rhodamine B. Acetyl(per)oxyl radicals were the dominant species in this novel system. The addition of 2,4-hexadiene (2,4-HD) and Methanol (MeOH) significantly inhibited the degradation efficiency of Rhodamine B. The ≡Cu2+/≡Cu+redox cycle dominated PAA activation, thereby producing organic radicals (R-O˙) including CH3C(O)O˙ and CH3C(O)OO˙, which accounted for the degradation of Rhodamine B. Increasing either the concentration of CuFe2O4(0–100 mg/L) or PAA (10–100 mg/L) promoted the removal efficiency of this potent system. In addition, weakly acid to weakly alkali pH conditions (6–8) were suitable for pollutant removal. The addition of Humid acid (HA), HCO3−, and a small amount of Cl−(10–100 mmol·L−1) slightly inhibited the degradation of Rhodamine B. However, degradation was accelerated by the inclusion of high concentrations (200 mmol·L−1) of Cl−. After four iterations of catalyst recycling, the degradation efficiency remained stable and no additional functional group characteristic peaks were observed. Taking into consideration the reaction conditions, interfering substances, system stability, and pollutant-removal efficiency, the CuFe2O4/PAA system demonstrated great potential for the degradation of Rhodamine B.Keywords:peracetic acid (PAA);rhodamine B;copper ferrite (CuFe2O4);organic radicals (R-O˙)
研究领域:
环境科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Shuting Liu,Guorui Liu,Mingxuan Wang,Linjun Qin,Qingyu Guo,Da Li,Lili Yang,Minghui Zheng
The inhibition of organic pollutants in thermal industrial systems, where metal catalysts and organic pollutant precursors coexist, requires mechanistic insights for targeted control. This study elucidates detailed inhibition mechanisms of ammonium sulfate suppresses toxic byproducts in widespread copper-catalyzed reactions from the micro perspectives of organic free radicals through dual pathways: (1) Organic radical regulation: In-situ EPR identified ortho -amino-tetrachlorophenoxy radicals as key intermediates, which resist dimerization into toxic products. The identified radical structure provides direct evidence supporting the proposed molecular mechanisms. (2) Catalyst deactivation: X-ray analysis demonstrated ammonium sulfate's occupation of Cu active sites and reduction of catalytic oxidation states. These findings provide a molecular-level framework for inhibiting pollutants in metal-rich industrial processes.
研究领域:
环境科学
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化学
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DOI
高影响因子
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2024
·Vol. 121
·期 23
·e2403544121
·
IF 9.4
Jing-Hang Wu,Tian-Hao Yang,Yi-Jiao Sun,Yuan Min,Yi Hu,Fei Chen,Jie-Jie Chen,Han-Qing Yu
Peracetic acid (PAA) is emerging as a versatile agent for generating long-lived and selectively oxidative organic radicals (R–O•). Currently, the conventional transition metal–based activation strategies still suffer from metal ion leaching, undesirable by-products formation, and uncontrolled reactive species production. To address these challenges, we present a method employing BiOI with a unique electron structure as a PAA activator, thereby predominantly generating CH3C(O)O• radicals. The specificity of CH3C(O)O• generation ensured the superior performance of the BiOI/PAA system across a wide pH range (2.0 to 11.0), even in the presence of complex interfering substances such as humic acids, chloride ions, bicarbonate ions, and real-world water matrices. Unlike conventional catalytic oxidative methods, the BiOI/PAA system degrades sulfonamides without producing any toxic by-products. Our findings demonstrate the advantages of CH3C(O)O• in water decontamination and pave the way for the development of eco-friendly water decontaminations based on organic peroxides.
研究领域:
环境科学
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化学
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DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2022
·
IF 11.357
Yixin Huang,Jing Zou,Jinbin Lin,Haoyu Yang,Mengyun Wang,Jiawen Li,Wei Cao,Baoling Yuan,Jun Ma
The activation of peroxydisulfate (PDS) by organic compounds has attracted increasing attention. However, some inherent drawbacks including quick activator decomposition and poor anti-interference capacity limited the application of organic compound-activated PDS. It was interestingly found that 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonate) (ABTS) could act as both activator and electron shuttle for PDS activation to enhance diclofenac (DCF) degradation over a pH range of 2.0–11.0. Multiple reactive species of ABTS•+, •OH, and SO4•– were generated in the PDS/ABTS system, while only ABTS•+ and •OH directly contributed to DCF degradation. ABTS•+, generated via the reactions of ABTS with PDS, SO4•–, and •OH, was the dominant reactive species of DCF degradation. No significant decomposition of ABTS was observed in the PDS/ABTS system, and ABTS acted as both activator and electron shuttle. Four possible degradation pathways of DCF were proposed, and the toxicity of DCF decreased after treatment with the PDS/ABTS system. The PDS/ABTS system had good anti-interference capacity to common natural water constituents. Additionally, ABTS was encapsulated into cellulose to obtain ABTS@Ce beads, and the PDS/ABTS@Ce system possessed excellent performance on DCF degradation. This study proposes a new perspective to reconsider the mechanism of activating PDS with organic compounds and highlights the considerable contribution of organic radicals on contaminant removal.
研究领域:
环境科学
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污染控制
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化学工程
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DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2024
·
IF 12.2
Ziyue Li,Xiaolei Wang,Fei Peng,Ning Chen,Guodong Fang
The use of peracetic acid (PAA) in advanced oxidation processes has gained significant attention recently, but the knowledge of activating PAA to degrade polycyclic aromatic hydrocarbons (PAHs) is limited due to the variety and selectivity of reactive substances in PAA oxidation system. This paper presented the first systemically study on the degradation of PAHs by PAA activation in soil. It was found that heat-activated peracetic acid (heat/PAA) was capable of degrading phenanthrene (PHE) efficiently with degradation efficiency > 90 % within 30 min. Experimental results demonstrated that a series of reactive oxygen species (ROS) including organic radicals (RO • ), hydroxyl radicals (HO • ) and singlet oxygen ( 1 O 2 ) were generated, while acetylperoxyl (CH 3 C(O)OO • ) and acetyloxyl (CH 3 C(O)O • ) radicals were primarily responsible for PHE degradation in soil. Further analysis shows that polymerization products such as diphenic acid , 2′-formyl-2-biphenylcarboxylic acid and other macromolecules were dominant products of PHE degradation, suggesting polymerization driving PHE degradation instead of the conventional mineralization process. Toxicity analysis shows that most of the polymerization products had less toxicity than that of PHE. These results indicate that PAA activation was a highly effective remediation method for PAHs contaminated soil, which also provided a novel mechanism for pollutant degradation with the PAA activation process for environmental remediation.
研究领域:
环境科学
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化学
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产品关联
DOI
PubMed
高影响因子
TALANTA
·
2023
·
IF 6.1
Yixuan Xu,Changchang Teng,Huiping Dang,Dalong Yin,Lifeng Yan
Stable organic radical molecules have received extensive attention due to their unique electronic structure and photophysical properties, and the highly fluorescent quantum efficiency has great appeal to bioimaging. However, still scarce reports on the application of them on the therapy of tumors, especially theranostics. Here, 3,6-dibromocarbazole modified tris (2,4,6-trichlorophenyl) methane radical (TB) has been synthesized with high NIR fluorescence quantum efficiency, and free radical nanoparticles (NPs) have been prepared using the precursor of the radical doping strategy. The free radical molecule TB and its precursor molecule HTB were mixed in proportion and encapsulated with an amphiphilic polypeptide (PEG-PAsp) to obtain the NPs. The 4% NPs can achieve a high fluorescence quantum efficiency (18.68%) in the NIR region. In addition, the NPs also have a good ability to produce reactive oxygen species (ROS) under either normoxia or hypoxia conditions, which makes it possible for photodynamic therapy (PDT). Interestingly, the NPs also show preferable photothermal ability (PCE = 42.39%) for photothermal therapy (PTT). Both in vitro and in vivo studies reveal that the as-prepared radical NPS show a NIR fluorescence imaging-guided synergistic PTT and type I/II PDT to tumors. It provides new strategies and new clues for the application of free radical molecules in the theranostics of tumors.
研究领域:
生物医学工程
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分子影像学
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肿瘤学
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产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2014
·
IF 4.086
Lihuan Xu,Fang Yang,Chang Su,Lvlv Ji,Cheng Zhang
Two 2,2,6,6-tetramethylpiperidinyl-N-oxy (TEMPO) contained polypyrrole (PPy) derivatives with the different side-chain length were synthesized by esterification of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radial with pyrrole butyric acid and pyrrole caproic acid. Then the homopolymers of 4-(3-(Pyrrol-1-yl)butyryloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-B-TEMPO) and 4-(3-(Pyrrol-1-yl)hexanoyloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-C-TEMPO) were prepared by chemical oxidative polymerization. The structure, morphology, electrochemical properties of prepared polymers were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet visible spectroscopy (UV-vis), scanning electron microscopy (SEM), cyclic voltammograms (CV) and electrochemical impedance spectra (EIS), respectively. Also, the charge-discharge properties of the prepared polymers were studied by galvanostatic charge-discharge testing. The results demonstrated that the as-synthesized nitroxide radical polymers showed a reversible two-electron redox reaction process in the potential limits of 2.5–3.0 V and 3.4–3.8 V vs Li/Li + , respectively. Under our experimental conditions, PPy only presented the discharge capacity of 16.5 mAh·g −1 at 20 mA·g −1 between 2.5 and 4.2 V, while PPy-B-TEMPO with the short side-chain linked to TEMPO groups exhibited an initial discharge capacity of up to 86.5 mAh·g −1 with two well-defined plateaus. Furthermore, the PPy-C-TEMPO with the longer linking side-chain even displayed a discharge capacity of 115 mAh·g −1 . These superior electrochemical performances were ascribed to the flexible linking side-chain and the introduction of stable conductive PPy main chain, which benefits the improvement of charge carrier transportation in the aggregated polymer bulk.
研究领域:
材料科学
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电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2022
·
IF 7.968
Gaofeng Zhou,Runyu Zhou,Yiqing Liu,Li Zhang,Linyue Zhang,Yongsheng Fu
A novel heterogeneous peracetic acid (PAA)-based advanced oxidation process (AOP), viz. zero-valent cobalt activated PAA (ZVCo/PAA), was developed to remove sulfamethoxazole (SMX) in this study. About 99% SMX could be removed by ZVCo/PAA under neutral condition in 5 min. According to the characterization results of ZVCo before and after reaction by scanning electron microscopy (SEM), ZVCo was corroded to provide Co 2+ which was primarily responsible for the activation of PAA. The X-ray photoelectron spectroscopy (XPS) analysis of fresh and used ZVCo suggested that heterogeneous catalysis also occurred on the surface of ZVCo. Radical scavenging experiments indicated that organic radicals (i.e., CH 3 C(O)O • and CH 3 C(O)OO • ) were the dominant reactive species for SMX degradation in ZVCo/PAA system. SMX could be degraded well in a wide pH range especially at near-neutral pH. Increasing PAA or ZVCo dosage could enhance SMX removal, while excess ZVCo inhibited its degradation. The addition of SO 4 2− , NO 3 − or Cl − had a negligible effect on SMX degradation, while an obvious inhibition was observed in the presence of HCO 3 − or natural organic matter (NOM). ZVCo still presented an excellent activation ability for PAA to degrade SMX after 4 cycles, indicating its good stability and reusability. The probable reaction sites in SMX molecular structure were predicted by density functional theory (DFT) calculation and wave function analysis. Combining the results of DFT calculation and five identified transformation products , four possible degradation pathways of SMX in ZVCo/PAA system were proposed, including nitration , cleavage of S-N bond, coupling reaction and hydroxylation.
研究领域:
环境科学
·
化学工程
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DOI
高影响因子
ADVANCED MATERIALS
·
2025
·
IF 26.8
Man Li,Xin Li,Ying-Feng Han
Organic luminescent radicals possess considerable potential for applications in organic light-emitting diodes (OLEDs)-based visible light communication owing to their intrinsic advantages of nanosecond emission lifetimes and spin-allowed radiative transitions. However, the inherently narrow energy bandgap and multiple nonradiative channels of organic radicals make it difficult to achieve efficient green and blue light-emitting, which is not conducive to applying visible light communication in diverse fields. In this study, a series of carbon-centered radicals derived from N-heterocyclic carbenes are designed and synthesized, some of which exhibiting hybrid local and charge-transfer (HLCT) states that resulting in efficient green emission. The results of photophysical characterizations and theoretical calculations demonstrate that the luminescence efficiency is closely related to their emission states. This relationship inhibits the nonradiative channels while simultaneously opening the radiative channels of organic radicals exhibiting HLCT states but not those with locally excited states. Intriguingly, a high photoluminescence quantum yield value of up to 70.1% at 534 nm is observed, which is the highest among green light-emitting carbon-centered radicals reported to date. Based on this exceptional result, an OLED device is fabricated and achieved an external quantum efficiency of 8.8%. These results demonstrate its potential application in electroluminescent devices.
研究领域:
材料科学
·
光学工程
·
化学
✓ 已验证
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DOI
PubMed
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 27
·22989-22995
·
IF 3.289
Chang Su,Lvlv Ji,Lihuan Xu,Ningning Zhou,Guosheng Wang,Cheng Zhang
A high free radical density polytriphenylamine derivative, poly(1-N,1-N,4-N-triphenyl-4-N-[4-(N-[4-(N-phenylanilino)phenyl]anilino)phenyl]benzene-1,4-diamine) (PFTP) has been synthesized and investigated as the cathode material of organic free radical batteries for the first time. The molecular structure, thermal-stability, morphology, spectral characteristics and electrochemical properties of the prepared polymer were characterized by Raman spectroscopy (RS), electron spin resonance (ESR), pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), MALDI-TOF mass spectrometry, thermogravimetric analysis (TGA), ultraviolet visible spectroscopy (UV-vis), scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Also, the charge–discharge properties of the prepared polymers were studied by galvanostatic charge–discharge testing. Compared to PTPA, it was found that PFTP not only had improved thermal stability and morphology, but also exhibited obvious four-electron redox characteristics. At a discharge current of 20 mA g−1, the PFTP electrode presented a multi-stage discharge platform and an improved discharge capacity of 74.2 mA h g−1 compared to PTPA, which could be attributed to the high free radical density and the improved morphology of the obtained novel polymer. The above exploratory work made it promising to design the multi-electron redox centers of the polytriphenylamine-based polymer to obtain improved electrochemical performance.
研究领域:
材料科学
·
电化学
·
高分子化学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yixuan Xu,Changchang Teng,Yating Wang,Dejia Chen,Dalong Yin,Lifeng Yan
Stable organic radicals have emerged as a promising option to enhance fluorescence quantum yield (QY), gaining traction in medical treatment due to their unique electronic transitions from the ground state (D 0 ) to the doublet excited state (D 1 ). We synthesized a stable dicyanomethyl radical with a NIR-II fluorescence QY of 0.86 %, surpassing many NIR-II organic dyes. Subsequently, amphiphilic polymer-encapsulated nanoparticles (NPs) containing the radical were created, achieving a NIR-II fluorescence QY of 0.32 %, facilitating high-contrast bio-imaging. These CNPPs exhibit self-enhanced photothermal properties, elevating photothermal conversion efficiency (PCE) from 43.5 % to 57.5 % under 915 nm laser irradiation. This advancement enables more efficient photothermal therapy (PTT) with lower dye concentrations and reduced laser power, enhancing both feasibility and safety. Through regular fractionated mild photothermal therapy, we observed the release of damage-associated molecular patterns (DAMPs) and an increase in cytokine expression, culminating in combined mild phototherapy (m-PTT)-mediated immunogenic cell death (ICD). Consequently, we developed an immunostimulatory tumor vaccine, showcasing a novel approach for refining photothermal agents (PTA) and optimizing the PTT process.
研究领域:
生物医学工程
·
纳米技术
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癌症治疗
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免疫疗法
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）