ABSTRACT
Phenylselenide based BODIPY probe was successfully synthesized and characterized by NMR spectroscopic techniques (1H, 13C and 77Se NMR), mass spectrometry and single crystal XRD. Surprisingly, crystal packing diagram of the probe showed formation of 1-D strip through intermolecular F---H interaction. The probe was screened with various Reactive Oxygen Species (ROS) and found to be selective for superoxide ion over other ROS via "turn-on" fluorescence response. The probe selectively and sensitively detects superoxide with a lower detection limit (43.34 nM) without interfering with other ROS. The quantum yield of the probe was found to increase from 0.091 % to 30.4 % (334-fold) after oxidation. Theoretical calculations (DFT and TD-DFT) were also performed to understand the sensing mechanism of the probe. The probe was able to effectively detect superoxide inside living cells without any toxic effect.
Subject(s)
Boron Compounds , Fluorescent Dyes , Organoselenium Compounds , Boron Compounds/chemistry , Boron Compounds/chemical synthesis , Humans , Organoselenium Compounds/chemistry , Organoselenium Compounds/chemical synthesis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Molecular Structure , Density Functional Theory , Superoxides/analysis , HeLa Cells , Reactive Oxygen Species/metabolism , Reactive Oxygen Species/analysisABSTRACT
Selenium-coumarin based probe 4 was synthesized from the reaction of a bromo derivative of coumarin with in situ prepared sodium phenyl selenide. Esterification of probe 4 resulted in the formation of probe 5. In the single crystal X-ray structure of probe 4, the phenylselenide group was placed parallel to the coumarin moiety whereas in probe 5, the phenylselenide group was perpendicular to the coumarin group. Hydrogen bonding interactions have been observed in the crystal packing of both the probes. Both the probes selectively detect superoxide over other reactive oxygen species (ROS). A kinetic study of the probes was performed, which suggested that probe 4 achieved maximum fluorescence intensity in less than 1 s while probe 5 required 30 min to attain maximum fluorescence intensity. Both probes 4 and 5 showed 37 fold and 48 fold increase in fluorescence intensity after the reaction with superoxide, respectively. The detection limits of probes 4 and 5 were found to be 46.4 nM and 48.9 nM, respectively. Both the probes showed reversibility with biothiols such as glutathione (GSH) and N-acetyl-L-cysteine (NAC). Probe 5 underwent more redox cycles with GSH compared to probe 4.
Subject(s)
Fluorescent Dyes , Superoxides , Coumarins/chemistry , Cysteine/chemistry , Fluorescent Dyes/chemistry , Glutathione/chemistry , Spectrometry, Fluorescence , X-RaysABSTRACT
A BOPHY-based organotellurium-containing probe was synthesized and characterized via single crystal XRD for the selective and sensitive detection of Hg2+ over other metal ions. The probe detects Hg2+ in less than 1 s with a 2.5-fold enhancement in fluorescent intensity. Due to the chalcogenophilicity of mercury, Hg2+ was facilely trapped in the NTe2 chelating cavity of the probe. The probe can detect Hg2+ in the nanomolar range (62 nM) and it showed reversibility with S2- ions. The sensitivity of the probe for the detection of Hg2+ was confirmed in living HeLa cells.
Subject(s)
Fluorescent Dyes , Mercury , Fluorescent Dyes/chemistry , HeLa Cells , Humans , Mercury/chemistry , Spectrometry, FluorescenceABSTRACT
Mercury ions are toxic and exhibit hazardous effects on the environment and biological systems, and thus demand for the selective and sensitive detection of mercury has become considerably an important issue. Here, we have developed a diselenide containing coumarin-based probe 3 for the selective detection of Hg(II) with a "turn-on" response (a 48 fold increase in fluorescence intensity) at 438 nm. The probe could quantitatively detect Hg(II) with a detection limit of 1.32 µM in PBS solution. Moreover, the probe has operable efficiency over the physiological range with an increase in the quantum yield from 1.2% to 57.3%. The reaction of the probe with Hg(II) yielded a novel monoselenide based coumarin 4via diselenide oxidation, which was confirmed by single crystal XRD. Furthermore, the biological use of the probe for the detection of Hg(II) was confirmed in the MCF-7 cell line. To the best of our knowledge, this is the first reaction-based probe for Hg(II) via diselenide oxidation.
Subject(s)
MercuryABSTRACT
Phenylselenide substituted BOPHY probes (BOPHY-SePh and PhSe-BOPHY-SePh) were synthesized and characterized by NMR spectroscopy and single-crystal XRD. Both the probes selectively detect HOCl in water with high sensitivity over other reactive oxygen species. A fluorescence "turn-on" event was attained due to cease of the PET process through transformation of selenide to selenoxide. Both the probes react with HOCl in less than 1 s. PhSe-BOPHY-SePh probe depicted low background fluorescence due to presence of two phenylselenide groups at BOPHY. PhSe-BOPHY-SePh probe has a low detection limit (0.63 µM) than BOPHY-SePh probe (1.08 µM). The bioimaging studies of both the probes were carried out in MCF 7 cells. Both the probes exhibited a good fluorescence response for HOCl in vitro and in mammalian cells. In addition, the probes showed reversibility with all bio-thiols, which was validated in MCF 7 cells using GSH.