Coumarin-Cu(II) Ensemble-Based Cyanide Sensing Chemodosimeter

Department of Chemistry, Korea University, Seoul, 136-704, Korea.
Organic Letters (Impact Factor: 6.36). 08/2011; 13(19):5056-9. DOI: 10.1021/ol2018856
Source: PubMed


An "ensemble"-based chemodosimeter 1-Cu(II) for cyanide detection is reported. 1-Cu(II) can recognize a cyanide ion over other anionic species to show a marked fluorescence enhancement under aqueous conditions. "Off-on" fluorescence change of 1-Cu(II) is proceeded by addition of cyanide, which induces decomplexation of the Cu(II) ion from nonfluorescent 1 followed by hydrolytic cleavage of the resulted Schiff base to give a strongly fluorescent coumarinaldehyde (2). The selective detection of cyanide with 1-Cu(II) for biological application was also performed in HepG2 cells.

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    • "A variety of fluorophores have been applied in constructing cyanide sensor, such as coumarin [48] [49] [50], BODIPY [51] [52] [53] and oxazine [54] [55], but their green to yellow emission wavelength (450–550 nm) limited the application in bioimaging. Cyanine [56] and hemicyanine [57] dyes were also applied, however, few of them displayed " off–on " fluorescence emission [58] [59] [60] [61] [62]. "
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    ABSTRACT: Two chemodosimeters PDMI and PMI for cyanide detection were designed and synthesized based on phenazine-cyanine dyes with N-methyl indolium group as receptor unit. According to the specific reactivity of indolium CN+ bond against cyanide anion, both of them featured high sensitivity with detection limit of 1.4 μM and 200 nM, respectively, and high selectivity against other anions. The quenching effect on phenazine-cyanine fluorophore by strong intramolecular charge transfer (ICT) from phenazine donor to indolium receptor made both PDMI and PMI non-emissive at the original state. After addition of cyanide, the ICT effect decreased and vanished leading to dramatic “off-on” fluorescence enhancement. PDMI which proceeded bilateral electrophilic reaction toward cyanide anion provided an emission signal at 580 nm in HEPES buffer with naked-eye detectable color change. Probe PMI utilized an unreactive formyl group instead of one reactive N-methyl indolium group as the electron-withdrawing component. Due to the unilateral recognition process for cyanide the ICT orientation of PMI was redirected thus exhibited fluorescence enhancement with maximum emission at 630 nm. Meanwhile, PMI was applied for monitoring intracellular cyanide in Hela cells and proved to achieve “off-on” fluorescent signal confirmed by confocal laser scanning microscopic imaging.
    Full-text · Article · Nov 2014 · Sensors and Actuators B Chemical
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    • "Thus, the sensitive and selective detection of cyanide anion is of considerable importance and significant interest. Up to date, there were various analysis methods for cyanide such as titrimetric [16], voltammetric [17], chromatographic methods [18], electrochemical devices [19] [20], colorimetric [21] [22] [23] and fluorimetric [24] [25] [26] [27] [28] [29] [30] [31] [32]. Among above strategies, fluorescent sensors present many appealing advantages, including high sensitivity, rapid response, low cost, easy detection and ease of application [33] [34] [35]. "
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    ABSTRACT: A new compound was conveniently synthesized via the condensation of 2-hydroxy-1,3,5-benzenetricarbaldehyde (1) with 1-methyl-2,3,3-trimethyl-3H-indolium (2) in ethanol. Its recognition ability was firstly carried out in DMSO. After addition of all kinds of anions, only CN− can induce a turn on fluorescence accompanying a blue-green fluorescence color. The mechanism is based on nucleophilic addition reaction of cyanide anion with the polarized CN bond of the indolium group blocking the π-conjugation between indolium and 2-hydroxy-1,3,5-benzenetricarbaldehyde, which was proved by H NMR and ESI-MS. In addition, the detection was completed with 2 min and the detection limit was found to be 45 nmol/L.
    Full-text · Article · Mar 2014 · Sensors and Actuators B Chemical
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    ABSTRACT: A new ratiometric fluorescent cyanide probe was developed based on the nucleophilic attack of CN(-) toward the indolium group of a hybrid coumarin-hemicyanine dye, by which high selectivity as well as large emission shift could be achieved.
    No preview · Article · Nov 2011 · Chemical Communications
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