Ratiometric fluorescent sensor based on inhibition of resonance for detection of cadmium in aqueous solution and living cells

L Xue, G Li, Q Liu, H Wang, C Liu, X Ding, S He… - Inorganic …, 2011 - ACS Publications
L Xue, G Li, Q Liu, H Wang, C Liu, X Ding, S He, H Jiang
Inorganic chemistry, 2011ACS Publications
Although cadmium has been recognized as a highly toxic heavy metal and poses many
detrimental effects on human health, the Cd2+-uptake and nosogenesis mechanisms are
still insufficiently understood, mainly because of the lack of facile analytical methods for
monitoring changes in the environmental and intracellular Cd2+ concentrations with high
spatial and temporal reliability. To this end, we present the design, synthesis, and
photophysical properties of a cadmium sensor, DQCd1 based on the fluorophore 4 …
Although cadmium has been recognized as a highly toxic heavy metal and poses many detrimental effects on human health, the Cd2+-uptake and nosogenesis mechanisms are still insufficiently understood, mainly because of the lack of facile analytical methods for monitoring changes in the environmental and intracellular Cd2+ concentrations with high spatial and temporal reliability. To this end, we present the design, synthesis, and photophysical properties of a cadmium sensor, DQCd1 based on the fluorophore 4-isobutoxy-6-(dimethylamino)-8-methoxyquinaldine (model compound 1). Preliminary investigations indicate that 1 could be protonated under neutral media and yield a resonance process over the quinoline fluorophore. Upon excitation at 405 nm, 1 shows a strong fluorescence emission at 554 nm with a quantum yield of 0.17. Similarly, DQCd1 bears properties comparable to its precursor. It exhibits fluorescence emission at 558 nm (Φf = 0.15) originating from the monocationic species under physiological conditions. Coordination with Cd2+ causes quenching of the emission at 558 nm and simultaneously yields a significant hypsochromic shift of the emission maximum to 495 nm (Φf = 0.11) due to inhibition of the resonance process. Thus, a single-excitation, dual-emission ratiometric measurement with a large blue shift in emission (Δλ = 63 nm) and remarkable changes in the ratio (F495 nm/F558 nm) of the emission intensity (R/R0 up to 15-fold) is established. Moreover, the sensor DQCd1 exhibits very high sensitivity for Cd2+ (Kd = 41 pM) and excellent selectivity response for Cd2+ over other heavy- and transition-metal ions and Na+, K+, Mg2+, and Ca2+ at the millimolar level. Therefore, DQCd1 can act as a ratiometric fluorescent sensor for Cd2+ through inhibition of the resonance process. Confocal microscopy and cytotoxicity experiments indicate that DQCd1 is cell-permeable and noncytotoxic under our experimental conditions. It can indeed visualize the changes of intracellular Cd2+ in living cells using dual-emission ratiometry.
ACS Publications
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