SENSORS AND ACTUATORS B-CHEMICAL
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2022
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IF 9.221
Kun Yu,Guangyao Zhang,Huining Chai,Lijun Qu,Dan Shan,Xueji Zhang
Metal−organic frameworks (MOFs) have emerged as promising materials for smart sensing and imaging applications. Here, a novel micron-biscuit Mn(III)-based porphyrinic MOF is synthesized with the modulation of 4,4′-biphenyldicarboxylic acid (BPDC). The anisotropic growth of MOF is induced by the increased steric hindrance , yielding micron-biscuit Mn-TCPP(BPDC) MOF crystals. Mn(III), as a sealer, quenched the intrinsic fluorescence of porphyrin because of the ligand-to-metal charge transfer (LMCT) effect, and this disappeared fluorescence can be regularly restored and enhanced due to LMCT effect inhibition and release of free porphyrin derived from the water-induced two-stage ligand exchange (TSLE) between BPDC, porphyrin and water. The as-prepared MOF acts as an excellent “signal-on” luminescent water-sensing probe with low amount (2.5 μg/mL) that can efficiently realize the trace detection of water in various organic media with high sensitivity, especially in dimethyl sulfoxide (DMSO), the detection limit is as low as 0.04% (v/v). Moreover, Mn-TCPP(BPDC) was successfully used for sensing water content in real commercial samples. This MOF with the guest-induced TSLE not only provides inspiration for the design of new luminescent materials, but also widens the path for smart sensing.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
CHEMOSPHERE
·
2018
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IF 4.427
Xinghao Wang,Jiayi Yao,Siyuan Wang,Xiaoxue Pan,Ruiyang Xiao,Qingguo Huang,Zunyao Wang,Ruijuan Qu
Photodegradation of pollutants is classically explained by reaction with reactive oxygen species. However Mn(III) may also remove pollutants, but direct evidence is actually lacking. Here we investigated the role of soluble Mn(III) on phototransformation of four typical estrogens, namely estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2), in the presence of Mn(II) and humic acid . Conversion rates of 60.2%, 89.0%, 87.6%, and 80.2% were achieved for E1, E2, E3, and EE2, respectively, after 72 h visible light irradiation. A detailed quenching experiments revealed that soluble Mn(III), and not reactive oxygen species, was the oxidant responsible for estrogen removal. The determination of Mn(III) concentration provided direct proof of the role of Mn(III)-based oxidizers in the conversion of estrogens. Soluble Mn(III) can form complexes with humic acid, and about 6.51 μM of Mn(III)-humic acid was formed from 20 μM of Mn(II) in the presence of 5 mg/L of humic acid. Furthermore, product identification and theoretical computation demonstrated that estrogens are mainly converted into oligomers (dimers, trimers, tetramers, etc.) via a single-electron process. According to these results, the oxidation of Mn(II) to Mn(III) is initiated by superoxide ion (O 2 •- ) generated from dissolved oxygen in the presence of humic acid under visible light irradiation. The formed soluble Mn(III) strips the estrogens of a single electron to generate phenoxyl radicals, which undergo oligomerization, while leads to regeneration of Mn(II). Hence, the photochemical Mn(II)-Mn(III) redox cycling may significantly influence the fate and transformation of estrogens in waters.
研究领域:
环境科学
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生物学
✓ 已验证
DOI
高影响因子
Journal of Earth Science
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2019
·Vol. 30
·期 4
·861-869
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IF 1.784
Zhang Caixiang,Liao Xiaoping,Lü You,Nan Chao
The ligand-stabilized soluble Mn(III) recognized as active intermediate can potentially mediate the attenuation of contaminants. In this study, the abiotic degradation behaviors of methyl parathion in the ligand stabilized Mn(III)-sulfite system were investigated. The results showed that the yield of soluble Mn(III) produced from the redox reaction of MnO 2 and oxalic acid was dependent linearly on the dosage of MnO 2 and caused the decomposition of methyl parathion up to 50.1% in Mn(III)-sulfite system after 30 minutes. The fitted pseudo-first-order reaction constants of methyl parathion degradation increased with the increasing of the amount of produced Mn(III) but was not effected linearly by the addition of sulfite. Other ligands, including pyrophosphate and oxalic acid, acted as effective complexing agents to stabilize soluble Mn(III), and exhibited competitive effect on methyl parathion degradation with sulfite. The formation of Mn(III)-sulfite complexes is the critical step in the system to produce abundant reactive oxygen species identified as SO 3 • - to facilitate methyl parathion degradation. The hydrolysis and oxidation of methyl parathion were acknowledged as two primary transformation mechanisms in Mn(III)-sulfite system. These findings indicate that naturally ligands-stabilized soluble Mn(III) can be generated and could oxidatively decompose organophosphate pesticides such as methyl parathion.
研究领域:
环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
MATERIALS RESEARCH BULLETIN
·
2019
·
IF 3.355
Lijun Zhu,Hao Cheng,Jianfeng Ma,Yong Kong,Yong Qin,Sridhar Komarneni
Decolorization of methyl orange (MO) by MnO 2 was investigated with and without small molecules of organic acids such as formic acid. It was found that the decolorization could be significantly improved by MnO 2 with the assistance of organic acids. The effect of various conditions was investigated on MO decolorization by using different crystal types of MnO 2 and changing the types of organic acids. One of the optimum treatment conditions was δ-MnO 2 /formic acid system, which led to the removal efficiency of 90.6% at 30 min. The pseudo-second-order kinetic rate constant of δ-MnO 2 /formic acid was 0.1626. A reasonable decolorization mechanism involving Mn(III) species was proposed and the mechanism was validated by simple detection of ionic species such as, Mn(II) and Mn(III) during the reaction. The δ-MnO 2 /formic acid process designed here may lead to a new advanced oxidation technology based on the in-situ generation of active Mn(III) species and their ability for oxidation.
研究领域:
环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
WATER RESEARCH
·
2017
·
IF 6.942
Erdan Hu,Ya Zhang,Shuyan Wu,Jun Wu,Liyuan Liang,Feng He
Mn(III) is a strong oxidant for one electron transfer , which may be important in the transformation of organic contaminants during water/wastewater treatment and biogeochemical redox processes. This study explored the reaction mechanisms of dissolved Mn(III) with organics. The role of dissolved Mn(III) either as a catalyst or an oxidant in reactions with organics was recognized. Aquo and/or hydroxo (or free) Mn(III), generated from the bisulfite activated permanganate process, facilitated efficient N-dealkylation of atrazine via a β-elimination mechanism, resulting no net redox reaction. In contrast, free Mn(III) degraded 4-chlorophenol via intramolecular redox processes, the same as hydroxyl radical ( OH), resulting in dechlorination , OH substitution, ring-opening and mineralization. Mn(III)-pyrophosphate compounds did not react with atrazine because complexation by pyrophosphate rendered Mn(III) unable to bond with atrazine, thus the electron and proton transfers between the reactants couldn't occur. However, it degraded 4-chlorophenol at a slower rate compared to free Mn(III), due to its reduced oxidation potential. These results showed two distinct mechanisms on the degradation of organic contaminants and the insights may be applied in natural manganese-rich environments and water treatment processes with manganese compounds .
研究领域:
环境科学
·
化学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
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2011
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IF 2.243
Shichao Xu,Wenwen Liu,Bingcheng Hu,Wei Cao,Zuliang Liu
A novel, sensitive and high selective flow-injection chemiluminescence (FI-CL) method for the determination of phenol is reported, based upon its decreasing effect on the CL reaction of luminol with hydrogen peroxide catalyzed by manganese (III) deuteroporphyrin [MnDP, Scheme 1 , 3 ] in alkaline solution. Under the selected optimized experimental conditions, the relative CL intensity was linear with phenol in the range of 4.0 × 10 −9 to 4.0 × 10 −7 g mL −1 . The detection limit (3 σ ) was 6.3 × 10 −10 g mL −1 and the relative standard deviation for 1.0 × 10 −7 g mL −1 phenol ( n = 11) was 2.99%. The regression equation was I = 120.79 + 1.14 × 1010 c ( R = 0.9936). This method has been applied to the determination of phenol in water with satisfactory results.
研究领域:
分析化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2015
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IF 5.33
Bo Sun,Xiaohong Guan,Jingyun Fang,Paul G. Tratnyek
MnO4– was activated by HSO3–, resulting in a process that oxidizes organic contaminants at extraordinarily high rates. The permanganate/bisulfite (PM/BS) process oxidized phenol, ciprofloxacin, and methyl blue at pHini 5.0 with rates (kobs ≈ 60–150 s–1) that were 5–6 orders of magnitude faster than those measured for permanganate alone, and ∼5 to 7 orders of magnitude faster than conventional advanced oxidation processes for water treatment. Oxidation of phenol was fastest at pH 4.0, but still effective at pH 7.0, and only slightly slower when performed in tap water. A smaller, but still considerable (∼3 orders of magnitude) increase in oxidation rates of methyl blue was observed with MnO2 activated by HSO3– (MO/BS). The above results, time-resolved spectroscopy of manganese species under various conditions, stoichiometric analysis of pH changes, and the effect of pyrophosphate on UV absorbance spectra suggest that the reactive intermediate(s) responsible for the extremely rapid oxidation of organic contaminants in the PM/BS process involve manganese(III) species with minimal stabilization by complexation. The PM/BS process may lead to a new category of advanced oxidation technologies based on contaminant oxidation by reactive manganese(III) species, rather than hydroxyl and sulfate radicals.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
WATER RESEARCH
·
2023
·
IF 12.8
Zhicheng Liao,Huan He,Danni Cui,Jingye Cui,Xiaoxia Yang,Ziwei Guo,Hao Chen,Guohua Dao,Bin Huang,Hongwen Sun,Xuejun Pan
Algal extracellular organic matter (EOM), a major fraction of the dissolved organic matter found in eutrophic plateau lakes, can act as a photosensitizer to drive the abiotic oxidation of Mn(II). This process has the potential to generate reactive Mn(III) and influence the fate of organic pollutants. In this study, the photodegradation of 17α-ethinylestradiol (EE2) in the presence of Mn(II) and EOM was investigated with emphasis on the photogeneration mechanism of Mn(III). The results indicated that Mn(II) can accelerate EE2 photodegradation in EOM solution owing to the photogeneration of reactive Mn(III), and the enhancement was greater at higher Mn(II) concentrations. The generation of reactive Mn(III) was mainly attributable to the action of superoxide radical generated by photosensitization of EOM. In addition, the photodegradation of EE2 was slower at higher pH, possibly because of the deactivation of Mn(III) under alkaline conditions. Single-electron transfer was an indispensable process in the photodegradation. The differences in fluorophore content, pH, and NO 3 − concentrations are all important determinants for EE2 photodegradation in natural waters. The information obtained in this research would contribute to the understanding of reactions between Mn(II) and EOM, and provide new insights into the behaviors of reactive Mn(III) in eutrophic water irradiated by sunlight.
研究领域:
环境科学
·
水污染治理
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产品关联
DOI
PubMed
高影响因子
Metallomics
·
2021
·Vol. 13
·期 3
·
IF 4.526
Li Jiayu,Wei Jingjing,Gao Zhonghong,Yin Guochuan,Li Hailing
Understanding the toxicological properties of MnIII-porphyrins (MnTPPS, MnTMPyP, or MnTBAP) can provide important biochemical rationales in developing them as the therapeutic drugs against protein tyrosine nitration-induced inflammation diseases. Here, we present a comprehensive understanding of the pH-dependent redox behaviors of these MnIII-porphyrins and their structural effects on catalyzing bovine serum albumin (BSA) nitration in the presence of H2O2 and NO2−. It was found that both MnTPPS and MnTBAP stand out in catalyzing BSA nitration at physiologically close condition (pH 8), yet they are less effective at pH 6 and 10. MnTMPyP was shown to have no ability to catalyze BSA nitration under all tested pHs (pH 6, 8, and 10). The kinetics and active intermediate determination through electrochemistry method revealed that both the pH-dependent redox behavior of the central metal cation and the antioxidant capability of porphin derivative contribute to the catalytic activities of three MnIII-porphyrins in BSA nitration in the presence of H2O2/NO2−. These comprehensive studies on the oxidative reactivity of MnIII-porphyrins toward BSA nitration may provide new clues for searching the manganese-based therapeutic drugs against the inflammation-related diseases.
研究领域:
生物化学
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药理学
·
炎症研究
✓ 已验证
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2019
·
IF 7.149
Xinghao Wang,Wenrui Xiang,Siyuan Wang,Jiali Ge,Ruijuan Qu,Zunyao Wang
Soluble manganese(III), stabilized by ligands as Mn(III)-L complexes, are ubiquitous in natural waters and wastewaters and can potentially serve as both the oxidant and reductant in one-electron transfer reactions with organic contaminants. In this study, the oxidative transformations of 14 phenolic endocrine disrupting chemicals (EDCs) by in situ-formed Mn(III)-L complexes, generated from irradiated water containing Mn(II) and humic acid, were investigated. The pseudo-first-order rate constants (kobs, h–1) of these phenols varied from 1.0 × 10–4 to 5.9 × 10–2. A quantitative structure–activity relationship model was developed, which suggests that the electron-donating ability (EHOMO) of phenolic chemicals was the most important molecular characteristic for the Mn(III)-L-mediated oxidative transformation. Phenol transformation was initiated by the generation of a phenoxyl radical through electron transfer to Mn(III)-L. Subsequent self-coupling reactions between phenoxyl radicals resulted in the formation of self-coupling dimers and trimers. With the addition of simple phenol as a cosubstrate, enhanced transformations of these phenolic EDCs were clearly observed, and cross-coupling products of simple phenol and the substrates were also detected. In addition, a reaction activation energy calculation based on the transition-state theory indicated that the cross-coupling reaction was more likely than the self-coupling reaction to occur in the presence of phenol. This work provides new insights into the environmental fate of phenolic compounds.
研究领域:
环境科学
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化学
·
生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FLUID PHASE EQUILIBRIA
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2014
·
IF 2.241
Chunlin Li,Qinbo Wang,Binwei Shen,Zhenhua Xiong,Chuxiong Chen
The solubility of 5,10,15,20-tetrakis(4-chlorophenyl) porphyrin manganese(III) chloride (abbreviated in p -ClTPPMnCl) in N , N -dimethylformamide (abbreviated in DMF) + water solvent mixtures at 293.2–353.2 K were measured. The effects of mass fraction of DMF in the solvent mixtures at 1.00–0.80 on the solubility were studied. The results show that the solubility decreases with the decreasing mass fraction of DMF at constant temperature, and increase with the increasing temperature at constant solvent composition. The experimental data were correlated with Apelblat equation, and the solubilities calculated by the model were in good agreement with experimental observations.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）