A mesoporous silica-based inorganic-organic hybrid material (NBD-AP-MCM) has been designed and developed as a fluorescent chemosensor for the detection of fluoride in aqueous medium. The system was developed by covalently anchoring 7-nitro-2,1,3-benzoxadiazole (NBD) dye onto the surface of mesoporous silica nanoparticles, MCM-41. The system was characterized using several conventional analytical methods comprising spectroscopic, microscopic and thermo-gravimetric techniques. The sensory action of the material was investigated by carrying out steady state absorbance, fluorescence and time resolved fluorescence studies on the system in the absence and presence of several biologically and environmentally important anions in aqueous solution. The photophysical data of the present system (NBD-AP-MCM) have also been compared with the free dye (NBD) molecules. A significant decrease in the fluorescence quantum yield of the fluorophore in the hybrid material NBD-AP-MCM has been observed as compared to the unbound NBD. The decrease in fluorescence efficiency in the hybrid material is attributed to the aggregation caused quenching (ACQ) phenomenon. Interestingly, the system displays more than six-fold fluorescence enhancement in the presence of fluoride ions in aqueous solution. Enhancement of the fluorescence lifetime of the fluorescing moiety (NBD) has also been observed during fluorescence time-resolved studies. No significant optical changes have been observed with other commonly encountered anions rendering the present system highly selective towards fluoride detection. The fluorescence enhancement has been attributed to the cleavage of Si-O bonds due to the addition of fluoride. The silyl cleavage detaches the fluorophore from the solid support thereby making the fluorophore "free" in solution, which in turn recovers its original fluorescence which was decreased because of the aggregation on the solid silica support. Furthermore, the suitability of the present system in cellular imaging has also been demonstrated.

We report herein the synthesis and photophysical studies on a new multicomponent chemosensor dyad comprising two fluorescing units, dansylamide (DANS) and nitrobenzoxadiazole (NBD). The system has been developed to investigate receptor-analyte binding interactions in the presence of both cations and anions in a single molecular system. A dimethyl amino (in the DANS unit) group is used as a receptor for cations, and acidic hydrogens of sulfonamide and the NBD group are used as receptors for anions. The system is characterized by conventional analytical techniques. The photophysical properties of this supramolecular system in the absence and presence of various metal ions and nonmetal ions as additives are investigated in an acetonitrile medium. Utility of this system in an aqueous medium has also been demonstrated. The absorption and fluorescence spectrum of the molecular system consists of a broad band typical of an intramolecular charge-transfer (ICT) transition. A low quantum yield and lifetime of the NBD moiety in the present dyad indicates photoinduced electron transfer (PET) between DANS and the NBD moiety. The fluorescence intensity of the system is found to decrease in the presence of fluoride and acetate anions; however, the quenching is found to be much higher for fluoride. This quenching behavior is attributed to the enhanced PET from the anion receptor to the fluorophore moiety. The mechanistic aspect of the fluoride ion signaling behavior has also been studied by infrared (IR) and (1)H NMR experiments. The hydrogen bonding interaction between the acidic NH protons of the DPN moiety and F(-) is found to be primarily responsible for the fluoride selective signaling behavior. While investigating the cation signaling behavior, contrary to anions, significant fluorescence enhancement has been observed only in the presence of transition-metal ions. This behavior is rationalized by considering the disruption of PET communication between DANS and the NBD moiety due to transition-metal ion binding. Theoretical (density functional theory) studies are also performed for the better understanding of the receptor-analyte interaction. Interestingly, negative cooperativity in binding is observed when the interaction of this system is studied in the presence of both Zn(2+) and F(-). Fluorescence microscopy studies also revealed that the newly developed fluorescent sensor system can be employed as an imaging probe in live cells.

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