Nilanjan Dey

Selective and Efficient Detection of Nitro-Aromatic Explosives in Multiple Media including Water, Micelles, Organogel, and Solid Support

Selective detection of nitro-aromatic compounds (NACs) at nanomolar concentration is achieved for the first time in multiple media including water, micelles or in organogels as well as using test strips. Mechanism of interaction of NACs with highly fluorescent p-phenylenevinylene-based molecules has been described as the electron transfer phenomenon from the electron-rich chromophoric probe to the electron deficient NACs. The selectivity in sensing is guided by the pKa of the probes as well as the NACs under consideration. TNP-induced selective gel-to-sol transition in THF medium is also observed through the reorganization of molecular self-assembly and the portable test trips are made successfully for rapid on-site detection purpose.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+ under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

Remarkable role of positional isomers in the design of sensors for the ratiometric detection of copper and mercury ions in water

Cation sensing properties of the three positional isomers of rhodamine based sensors (1–3) are studied in water. The sensors differ only in the position of pyridines nitrogen. The chemosensor 1, with pyridine nitrogen at ortho-position, showed a selective colorimetric detection of Cu(II) ions in water, at physiological pH 7.4 and also in medium containing BSA (bovine serum albumin) and blood serum. Notably the compound 2 and 3, with pyridine end located at meta- and para-positions did not show any color change with Cu(II) ions, although both the compounds showed turn-on change both in color and fluorescence with Hg(II) ions specifically. All the probes showed ratiometric changes with the specific metal ions. The changing position of nitrogen also changed the complexation pattern of the sensors with the metal ions. Probe 1 showed 2:1 complexation with Cu(II), whereas 2 and 3 showed 1:1 complexation with Hg(II) ions. The mechanism investigation showed that the change in color upon addition of metal ions is due to the ring-opening of the spirolactam ring of the probes. Cu(II) interacted with ligand 1 through a three-point interaction mode comprising carbonyl oxygen, amido nitrogen and pyridine nitrogen end. But in case of 2 and 3, Hg2+ only interacted through pyridine nitrogen ends. Quantitative estimation of Cu2+ and Hg2+ in complex biological media such as bovine albumin protein (BSA) and human blood serum were performed using these sensors. Rapid on-site detection as well as discrimination of these toxic ions was demonstrated using easily prepared portable test-strips.

Tunable Emission from Fluorescent Organic Nanoparticles in Water: Insight into the Nature of Self-Assembly and Photoswitching

Excitation-dependent tuning of the emission behavior of fluorescent organic nanoparticles (FONs) with two simple luminescent pyrenyl-pyridyl conjugates as model systems is demonstrated. In the case of the compound with a flexible bis-picolyl moiety, the simultaneous presence of multiple ground-state species with distinct absorption and emission characteristics can be observed. The relative ratios of these species can easily be modulated, and it is possible to selectively stimulate any one of them individually by choosing an appropriate excitation channel. Moreover, at high concentration, a drastic change in the nature of the self-assembly is observed, which shifts from donor-acceptor-type self-assembly to exciplex-type self-agglomeration. On the contrary, the compound containing a rigid terpyridine unit has only a single ground state and shows no such tunable emission. However, it can exhibit multiple emission bands in water, whereby the positions of their emission maxima depend on the extent of aggregation-induced planarization of the probe molecules. Overall, this work demonstrates multimodal modulation of FON emission and a gives insight into how molecular order can translate into complete switching of nanoparticle self-assembly and photophysics.

Motion-Induced Changes in Emission as an Effective Strategy for the Ratiometric Probing of Human Serum Albumin and Trypsin in Biological Fluids

Herein, we report the formation of a highly luminescent, pH-sensitive, thermoreversible nanoaggregate in pure aqueous medium through the self-agglomeration of carbazole-based amphiphiles. The self-assembly process restricted the intramolecular motion of the molecules and induced a change in its emission signal from blue to cyan, owing to an aggregation-induced emission (AIE) effect. A similar type of ratiometric response was also observed in the presence of human serum albumin (HSA). However, in this case, the molecular motion of the flexible fluorescent probe was restricted by its embedded microenvironment, owing to a motion-induced change in emission (MICE) effect, not by aggregation. Moreover, the probe showed quite high selectivity for HSA over other serum albumin proteins. Our carbazole-based fluorescent probes are a unique example of the ratiometric sensing of HSA through the sole involvement of reversible noncovalent interactions. Considering the important of HSA in clinical diagnosis, a wide range of biological fluids, such as human urine, saliva, and plasma, were screened to analyze their HSA content. In addition, this system was also employed for the detection of trypsin at subnanomolar concentrations through the digestion of HSA.