Fluorescent Chemosensors Based on Spiroring-Opening of Xanthenes and Related Derivatives Xiaoqiang Chen, Tuhin Pradhan, Fang Wang, Jong Seung Kim,* and Juyoung Yoon* Departments of Chemistry and Nano Science and of Bioinspired Science (WCU), Ewha Womans University, Seoul 120-750, Korea State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China Department of Chemistry, Korea University, Seoul 136-701, Korea

Fluorescent chemosensors based on spiroring-opening of xanthenes and related derivatives.

Reports that promote persulfate-based advanced oxidation process (AOP) as a viable alternative to hydrogen peroxide-based processes have been rapidly accumulating in recent water treatment literature. Various strategies to activate peroxide bonds in persulfate precursors have been proposed and the capacity to degrade a wide range of organic pollutants has been demonstrated. Compared to traditional AOPs in which hydroxyl radical serves as the main oxidant, persulfate-based AOPs have been claimed to involve different in situ generated oxidants such as sulfate radical and singlet oxygen as well as nonradical oxidation pathways. However, there exist controversial observations and interpretations around some of these claims, challenging robust scientific progress of this technology toward practical use. This Critical Review comparatively examines the activation mechanisms of peroxymonosulfate and peroxydisulfate and the formation pathways of oxidizing species. Properties of the main oxidizing species are scrutinized and the role of singlet oxygen is debated. In addition, the impacts of water parameters and constituents such as pH, background organic matter, halide, phosphate, and carbonate on persulfate-driven chemistry are discussed. The opportunity for niche applications is also presented, emphasizing the need for parallel efforts to remove currently prevalent knowledge roadblocks.

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Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks.

Advances in copper complexes as anticancer agents.

Select persulfate activation processes were demonstrated to initiate oxidation not reliant on sulfate radicals, although the underlying mechanism has yet to be identified. This study explored singlet oxygenation and mediated electron transfer as plausible nonradical mechanisms for organic degradation by carbon nanotube (CNT)-activated peroxymonosulfate (PMS). The degradation of furfuryl alcohol (FFA) as a singlet oxygen (1O2) indicator and the kinetic retardation of FFA oxidation in the presence of l-histidine and azide as 1O2 quenchers apparently supported a role of 1O2 in the CNT/PMS system. However, the 1O2 scavenging effect was ascribed to a rapid PMS depletion by l-histidine and azide. A comparison of CNT/PMS and photoexcited Rose Bengal (RB) excluded the possibility of singlet oxygenation during heterogeneous persulfate activation. In contrast to the case of excited RB, solvent exchange (H2O to D2O) did not enhance FFA degradation by CNT/PMS and the pH- and substrate-dependent reactivity of CNT/PMS ...

Identifying the Nonradical Mechanism in the Peroxymonosulfate Activation Process: Singlet Oxygenation Versus Mediated Electron Transfer

Heterogeneous Fenton reactions have gained widespread attention in removing recalcitrant organic contaminants as the reaction between solid Fenton catalysts and H2O2 can generate highly reactive hydroxyl radicals (HO[rad]). However, several drawbacks, such as the low-speed generation of Fe(II), high consumption of H2O2, and acidic reaction conditions (generally at ˜ pH 3), are always the core issues that hamper the large-scale application of heterogeneous Fenton reactions in environmental remediation. Thus, a large number of studies have been devoted to tackling these drawbacks, and this paper intends to comprehensively review the developed strategies for enhancing heterogeneous Fenton reactivity, mainly over the last decade. Based on a comprehensive survey of previous studies, we categorize these strategies according to their reaction mechanisms. For example, introducing additional electrons (e.g., from external electric fields, electron-rich materials, semiconductors, plasmonic materials, or doped metals) to heterogeneous Fenton catalysts can accelerate the generation of Fe(II); the in situ generation of H2O2 can be achieved by combining ultrasound, electricity, semiconductors, and iron-based catalysts in the system; and controlling the specific morphologies and exposed facets of heterogeneous Fenton catalysts can greatly promote the decomposition of H2O2. In addition, we briefly introduce some recent novel heterogeneous Fenton-like reactions that are of particular interest, including constructing dual reaction centers (i.e., the electron-poor center and the electron-rich center) and synthesizing single-atom catalysis-based heterogeneous Fenton-like catalysts. Moreover, this review article analyzes and compares the merits of each strategy for enhancing heterogeneous Fenton/Fenton-like reactions. We believe this review can motivate the construction of novel and efficient heterogeneous Fenton/Fenton-like systems and help readers choose proper Fenton/Fenton-like reaction systems for industrial applications.

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Strategies for Enhancing the Heterogeneous Fenton Catalytic Reactivity: A review

Film-based fluorescent sensor for visual monitoring and efficient removal of aniline in solutions and gas phase.

Methylmercury (CH3Hg+) recognition remains a challenging and imperative task due to its high toxicity and wide existence in the ecosystem. Herein, a novel fluorescent covalent-organic framework containing a boric acid functional group (COF-BA) was prepared by a postmodification strategy for CH3Hg+ detection. COF-BA served as a sensing platform for CH3Hg+ with fluorescence static quenching accompanied by fluorescence color changing from intense blue to colorless, and the detection limit was determined as 1.68 μM in a relatively narrow concentration range. COF-BA also exhibited superior selectivity toward CH3Hg+ detection. Furthermore, the spiked and recovery test in real water samples showed its efficient detection practicality. The detection mechanism of COF-BA toward CH3Hg+ was investigated. The recognitive boric acid group in COF-BA was first replaced by CH3Hg+. Then, the quinoline structure that served to limit the rotation of the imine bond was disrupted, leading to dramatic fluorescence quenching. The boric acid functional COF fluorescent probe can be a promising sensing platform for the detection of methylmercury and also provides new ideas for the construction of new fluorescent COF materials.

Boric Acid Functional Fluorescent Covalent-Organic Framework for Sensitive and Selective Visualization of CH3Hg.

A Novel Color-Coded Sensor Array for Visual Recognition and Traceability Investigation of Multiple Antibiotics

Ln(III) complexes with chromone-3-carbaldehyde-(2'-hydroxy)benzoyl hydrazone as the Schiff base ligand have been synthesised and characterised by elemental analysis, molar conductivity, H-1 NMR, mass spectra, UV-Vis spectra, and IR spectra. Electronic absorption spectra, fluorescence spectra, ethidium bromide displacement experiments and viscosity measurements indicate that the free ligand and its Ln(III) complexes, especially the La(III) complex, bind strongly to calf thymus DNA via an intercalation mechanism. The intrinsic binding constants of the free ligand, La(Ill) complex, Sm(III) complex and Er(III) complex with DNA were (2.20 +/- 0.12) x 10(5) M-1, (8.83 +/- 0.04) x 10(6) M-1, (7.35 +/- 0.07) x 10(6) M-1 and (3.24 +/- 0.04) x 10(6) M-1, respectively. Furthermore, the antioxidant activity of the ligand and its Ln(III) complexes was determined by the superoxide and hydroxyl radical scavenging method in vitro, which indicates that the ligand and its Ln(Ill) complexes are efficient antioxidants and the Ln(III) complexes exhibit more effective antioxidant activity than the free ligand alone and some standard antioxidants, such as mannitol and vitamin C.

Synthesis, characterisation, in vitro DNA binding properties and antioxidant activities of Ln(III) complexes with chromone-3-carbaldehyde-(2′-hydroxy) benzoyl hydrazone:

Yong Li

Papers

Film-based fluorescent sensor for visual monitoring and efficient removal of aniline in solutions and gas phase.

Boric Acid Functional Fluorescent Covalent-Organic Framework for Sensitive and Selective Visualization of CH3Hg.

A Novel Color-Coded Sensor Array for Visual Recognition and Traceability Investigation of Multiple Antibiotics

Synthesis, characterisation, in vitro DNA binding properties and antioxidant activities of Ln(III) complexes with chromone-3-carbaldehyde-(2′-hydroxy) benzoyl hydrazone:

A portable and intelligent logic detector for simultaneous and in-situ detection of Al3+ and fluoride in groundwater.