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A new coumarin-based fluorescent chemosensor, 3, incorporating a hydrazone (-NH-N=C-), was designed and synthesized. The chemosensor displayed higher affinity towards Fe3+ in water-acetonitrile solution in the presence of other competing cations in emission and absorption essays. The binding stoichiometry between the chemosensor 3 and Fe3+ was shown to occur in a 1:1 ratio, and the binding modes of the chemosensor towards Fe3+ were identified through the emission response, ¹H NMR, FT-IR and molecular modelling studies. The hydroxyl and amine functionalities on 3 were recognized as possible binding sites. The chemosensor presented a limit of detection, a limit of quantification and the association constant of 0.45 µM, 1.50 µM and 3.01 x 10¹ M-1, respectively. [ABSTRACT FROM AUTHOR]

Pollution caused by the release of toxic heavy metals into the environment by industrial and farming processes has been regarded as a major problem worldwide. This has attracted a great deal of attention into restoration and remediation. Mercury is classified as a toxic heavy metal which has posed significant challenges to public and environmental health. To date, conventional methods for mercury detection rely on expensive, destructive, complex, and highly specialized methods. Evidently, there is a need to develop systems capable of easily identifying and quantifying mercury within the environment. In this way, organic-based colorimetric chemosensors are gaining increasing popularity due to their high sensitivity, selectivity, cost-effectiveness, ease of design, naked-eye, and on-site detection ability. The formation of coumarin-azo derivative AD1 was carried out by a conventional diazotization reaction with coumarin-amine 1c and N,N-dimethylaniline. Sensor AD1 displayed remarkable visual colour change upon mercury addition with appreciable selectivity and sensitivity. The detection limit was calculated as 0.24 µM. Additionally, the reversible nature of AD1 allowed for the construction of an IMPLICATION type logic gate and Molecular Keypad Lock. Chemosensor AD1 displayed further sensing applications in real-world water samples and towards on-site assay methods. Herein, we describe a coumarin-derived chemosensor bearing an azo (N = N) functionality for the colorimetric and quantitative determination of Hg2+ in organic and aqueous media. [ABSTRACT FROM AUTHOR]

C9H9IO3, orthorhombic, Pnma (no. 62), a = 10.9655(5) Å, b = 6.5768(3) Å, c = 13.3770(6) Å, V = 964.7 Å3, Z = 4, Rgt(F) = 0.0130, wRref(F2) = 0.0350, T = 200 K.

The green hydrogen economy offers synthetic green energy with significant impacts and is environmentally friendly compared to current fossil-based fuels. Exploration of green hydrogen energy in Southern Africa is still in the initial stages in many low-resourced settings aiming to benefit from sustainable green energy. At this early stage, potential benefits to society are yet to be understood. That is why the socio-economic impact of green hydrogen energy must be explored. This paper reviews the current literatures to describe the potential socio-economic effects in the Southern African Development Community (SADC). The review supports the view that green hydrogen will be beneficial and have great potential to revolutionise agricultural and industrial sectors, with advanced sustainable changes for both production and processing. This paper also examines how sustainable green hydrogen energy production in Southern Africa will provide economic value in the energy export sector around the world and support climate change initiatives. Further, it discusses the impacts of the green hydrogen value addition chain and the creation of green jobs, as well as the need for corresponding investments and policy reforms. It is also noted that the green hydrogen economy can contribute to job losses in fossil fuel-based industries, so that the workforce there may need re-skilling to take up green jobs. Such exchanges may deter efforts towards poverty alleviation and economic growth in SADC. [ABSTRACT FROM AUTHOR]

A novel colorimetric and fluorometric method based on coumarin as signalling unit was developed for Hg2+ recognition and quantification. Initially, the alkyne functionality was incorporated into a coumarin system and the resulting molecule showed higher specificity and sensitivity for Hg2+ over other cations in both absorption and emission sensing assays. The Hg2+ recognition was detected as visible colour change from colourless to yellow and as fluorescence quenching. The colour change was assigned to the increased intramolecular charge transfer (ICT) in the signalling unit upon Hg2+ binding whereas a decline in the fluorescence intensity was ascribed to the heavy atom effect from Hg2+. In order to generate a material with high sensing performance level, alkyne-functionalized molecule was hosted into a polymeric material. The resulting functionalized polymer showed higher sensitivity and selectivity for Hg2+ over its corresponding coumarin molecule. The investigation of the possible binding modes for Hg2+ suggested both alkyne and triazole functionalities as potential binding sites for Hg2+. The limit of detection (LOD) and limit of quantification (LOQ) of the proposed method were evaluated and values less than a recommended maximum level of Hg2+contaminant in drinking water (2.00 μg/L) were obtained (LOD = 0.44 μg/L and LOQ = 1.33μg/L). The real-life application of the method was investigated using natural water samples containing Hg2+ levels equivalent to the maximum tolerable concentration of Hg2+ in drinking water. The outcomes suggested that the method could be used in the sensing and determination of Hg2+ level of contaminant in the environment. [ABSTRACT FROM AUTHOR]

A novel fluorescent polymer for Hg2+ recognition was developed based on the phototautomerism mechanism of 7-hydroxycoumarin in aqueous solution. The developed system showed higher sensitivity and specificity towards Hg2+ in the acetonitrile/water mixture over various other metal ions, with a significant fluorescence quenching of the main emission band. It was shown that the presence of Hg2+ affects the chemical equilibrium of the 7-hydroxycoumarin phototautomers through the excited state intramolecular proton transfer (ESIPT) mechanism, which results in ratiometric fluorescence response upon stepwise addition of Hg2+. The occurrence of ESIPT mechanism was explained based on a comparison of the 1H NMR spectra of the starting alkynylated coumarin (4) in a non-polar aprotic solvent (CDCl3) and in a polar aprotic solvent (DMSO-d6). This was further confirmed by 1H NMR of 4 upon stepwise addition of Hg2+ in a polar aprotic solvent (DMSO-d6). From titration experiments, a higher sensitivity with a detection limit at the nanomolar level (50 nM) was observed and the response was fast and reversible. The real applications of the developed system were investigated in real samples and satisfactory results were obtained for both fresh and lake water samples. [ABSTRACT FROM AUTHOR]

A novel fluorescent polymer with pendant triazolyl coumarin units was synthesized through radical polymerization. The polymer showed reasonable sensitivity and selectivity towards Cu2+ in acetonitrile in comparison to other tested metal ions with a significant quenching effect on fluorescence and blue shifting in the range of 20 nm. The blue shift was assigned to the conformation changes of the diethylamino group from the coumarin moiety which led to planarization of the triazolyl coumarin units. The possible binding modes for Cu2+ towards the polymer were determined through the comparison of the emission responses of the polymer, starting vinyl monomer and reference compound, and the triazole ring was identified as one of the possible binding sites for Cu2+. The detection limits of the polymer and vinyl monomer towards Cu2+ were determined from fluorescence titration experiments and a higher sensitivity (35 times) was observed for the polymer compared with its starting monomer. [ABSTRACT FROM AUTHOR]

C9H9IO3, orthorhombic, Pnma (no. 62), a = 10.9655(5) Å, b = 6.5768(3) Å, c = 13.3770(6) Å, V = 964.7 Å3, Z = 4, Rgt(F) = 0.0130, wRref(F2) = 0.0350, T = 200 K. [ABSTRACT FROM AUTHOR]

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A novel colorimetric and fluorometric method based on coumarin as signalling unit was developed for Hg2+ recognition and quantification. Initially, the alkyne functionality was incorporated into a coumarin system and the resulting molecule showed higher specificity and sensitivity for Hg2+ over other cations in both absorption and emission sensing assays. The Hg2+ recognition was detected as visible colour change from colourless to yellow and as fluorescence quenching. The colour change was assigned to the increased intramolecular charge transfer (ICT) in the signalling unit upon Hg2+ binding whereas a decline in the fluorescence intensity was ascribed to the heavy atom effect from Hg2+. In order to generate a material with high sensing performance level, alkyne-functionalized molecule was hosted into a polymeric material. The resulting functionalized polymer showed higher sensitivity and selectivity for Hg2+ over its corresponding coumarin molecule. The investigation of the possible binding modes for Hg2+ suggested both alkyne and triazole functionalities as potential binding sites for Hg2+. The limit of detection (LOD) and limit of quantification (LOQ) of the proposed method were evaluated and values less than a recommended maximum level of Hg2+contaminant in drinking water (2.00 μg/L) were obtained (LOD = 0.44 μg/L and LOQ = 1.33μg/L). The real-life application of the method was investigated using natural water samples containing Hg2+ levels equivalent to the maximum tolerable concentration of Hg2+ in drinking water. The outcomes suggested that the method could be used in the sensing and determination of Hg2+ level of contaminant in the environment. [ABSTRACT FROM AUTHOR]

A novel fluorescent polymer for Hg2+ recognition was developed based on the phototautomerism mechanism of 7-hydroxycoumarin in aqueous solution. The developed system showed higher sensitivity and specificity towards Hg2+ in the acetonitrile/water mixture over various other metal ions, with a significant fluorescence quenching of the main emission band. It was shown that the presence of Hg2+ affects the chemical equilibrium of the 7-hydroxycoumarin phototautomers through the excited state intramolecular proton transfer (ESIPT) mechanism, which results in ratiometric fluorescence response upon stepwise addition of Hg2+. The occurrence of ESIPT mechanism was explained based on a comparison of the 1H NMR spectra of the starting alkynylated coumarin (4) in a non-polar aprotic solvent (CDCl3) and in a polar aprotic solvent (DMSO-d6). This was further confirmed by 1H NMR of 4 upon stepwise addition of Hg2+ in a polar aprotic solvent (DMSO-d6). From titration experiments, a higher sensitivity with a detection limit at the nanomolar level (50 nM) was observed and the response was fast and reversible. The real applications of the developed system were investigated in real samples and satisfactory results were obtained for both fresh and lake water samples. [ABSTRACT FROM AUTHOR]

Two azo dyes, ( E )-3-(benzo[ d ]thiazol-2-yldiazenyl)-4-hydroxy-2 H -chromen-2-one (3CBD) and ( E )-4-hydroxy-3-(quinolin-2-yldiazenyl)-2 H -chromen-2-one (3CQD), were designed and synthesized using facile methods. The structures were validated through FTIR and NMR spectroscopy. The photophysical property analyses were further studied using UV-Vis and fluorescence spectrophotometers. Consequently, the absorption and emission spectra of 3CBD confirmed its selectivity of Hg 2+ and turn-off response to Fe 3+ . On the other hand, the absorption spectra analysis of 3CQD demonstrated selectivity in the presence of Hg 2+ . The colorimetric investigations demonstrated a significant visual response specifically for Hg 2+ , enabling real-time analysis in the corresponding solutions. The presence of other coexisting metal ions does not interfere with the detection of the target metal ion. The fluorescence studies of the two probes revealed that 3CBD was highly fluorescent, which was significantly quenched by Fe 3+ , upon excitation at 340 nm. Utilizing Job plot analyses, it was determined that the complexes 3CBD-Hg 2+ and 3CQD-Hg 2+ exhibit a binding stoichiometry of 1 : 1. The association constants for these complexes were measured to be 7.48 × 10 5 and 9.12 × 10 5 M -1 , respectively, indicating a strong association between both probes and their respective metal ions. Both chemosensors exhibited comparable limits of detection (LOD) and limits of quantification (LOQ) of 0.03 μM and 0.10 μM, respectively. Reversible studies confirmed that only chemosensor 3CQD could serve as a secondary sensor for EDTA. The theoretical studies calculated using Density Functional Theory (DFT) program at B3LYP/6-31G** (Spartan '10 package) level., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A novel fluorescent polymer with pendant triazolyl coumarin units was synthesized through radical polymerization. The polymer showed reasonable sensitivity and selectivity towards Cu 2+ in acetonitrile in comparison to other tested metal ions with a significant quenching effect on fluorescence and blue shifting in the range of 20 nm. The blue shift was assigned to the conformation changes of the diethylamino group from the coumarin moiety which led to planarization of the triazolyl coumarin units. The possible binding modes for Cu 2+ towards the polymer were determined through the comparison of the emission responses of the polymer, starting vinyl monomer and reference compound, and the triazole ring was identified as one of the possible binding sites for Cu 2+ . The detection limits of the polymer and vinyl monomer towards Cu 2+ were determined from fluorescence titration experiments and a higher sensitivity (35 times) was observed for the polymer compared with its starting monomer., Competing Interests: The authors declare no conflict of interest.