3 research outputs found

    Ligand Control of Copper-Mediated Cycloadditions of Acetylene to Azides: Chemo- and Regio-Selective Formation of Deutero- and Iodo-Substituted 1,2,3-Triazoles

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    The participation of σ-monocopper and σ-bis-copper acetylide in mechanistic pathways for copper-catalyzed cycloaddition (CuAAC) reactions of acetylene with azides was probed by analysis of deuterium distributions in the 1,2,3-triazole product formed by deuterolysis of initially formed mono- and bis-copper triazoles. The results show that, when Cu(Phen)(PPh3)2NO3 is used as the catalyst for reactions of acetylene with azides in DMF/D2O, 1-substituted-5-deutero-1,2,3-triazoles are generated selectively. This finding demonstrates that the Cu(Phen)(PPh3)2NO3-catalyzed cycloadditions utilize monocopper acetylide as the substrate and produce 5-copper-1,2,3-triazoles initially. Conversely, when DBU or Et3N is the copper ligand, the process takes place through initial formation and cycloaddition of bis-copper acetylide to produce 4,5-bis-copper-triazole, which reacts with D2O to form the corresponding 4,5-bis-deutero-triazole. Moreover, when C2D2 is used as the substrate, Cu(Phen)(PPh3)2NO3 as the Cu ligand, and H2O/DMF as the solvent, mono-C4-deutreo 1,2,3-triazoles are generated in high yields and excellent levels of regioselectivity. Lastly, CuAAC reactions of acetylene with azides, promoted by CuCl2·2H2O and NaI, yield 4,5-diiodo-1,2,3-triazoles with moderate to high efficiencies

    Engineering an Enzymatic Cascade Catalytic Smartphone-Based Sensor for Onsite Visual Ratiometric Fluorescence–Colorimetric Dual-Mode Detection of Methyl Mercaptan

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    Precise and reliable onsite detection of methyl mercaptan (CH3SH) is of great significance for environmental surveillance. Here, we synthesized a novel blue fluorescence nanozyme CeO2@TPE with high peroxidase-like activity by employing aggregation-induced emission (AIE) tetraphenylethene (TPE) to embed into hollow CeO2 nanospheres. In the presence of ethanol oxidase (AOX) and o-phenylenediamine (OPD), we engineered an enzymatic cascade activation ratiometric fluorescence–colorimetric dual-mode system AOX/CeO2@TPE + OPD toward CH3SH. In this design, CH3SH initiated AOX catalytic activity to convert it into H2O2 for activating the peroxidase-like activity of CeO2@TPE, producing •OH for oxidizing the naked-eye colorless OPD into deep yellow 2,3-diaminophenazine (DAP) with an absorption enhancement at ∼425 nm, companied by a new emission peak at ∼550 nm to match with the intrinsic emission at ∼441 nm for observing ratiometric fluorescence response, enabling a ratiometric fluorescence–colorimetric dual-mode analysis. Interestingly, both the ratiometric fluorescence and colorimetric signals could be gathered for being converted into the hue parameter on a smartphone-based sensor, achieving the onsite visual fluorescence–colorimetric dual-mode detection of CH3SH in real environmental media with acceptable results. This study gave a novel insight into designing target-responsive enzymatic cascade activation system-based efficient and reliable dual-mode point-of-care sensors for safeguarding environmental health
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