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.
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+.
A pyrene based amphiphilic receptor has been utilized in the nanomolar detection of uric acid at physiological pH in water. The compound shows a unique concentration-dependent modulation in optical response toward uric acid. In intramolecular/static excimer form (low concentration range), it displays a ratiometric response, while a "turn-off" sensing is observed specifically in the presence of intermolecular/dynamic excimer (high concentration range). The present protocol is then employed for the estimation of uric acid in blood serum samples of healthy individuals. Bland-Altman analysis in comparison to clinically approved uricase assay indicated the high accuracy of the present method. Additionally, the extent of insect infestation in stored grain samples was determined by measuring the uric acid content of their aqueous extracts. Low-cost color strips were developed for on-site detection of uric acid without involving any sophisticated instrument or trained personnel.
An easily synthesizable probe has been employed for dual mode sensing of glucosamine in pure water. The method was also applied for glucosamine estimation in blood serum samples and pharmaceutical tablets. Further, selective detection of glucosamine was also achieved using portable color strips.
Single-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled realtime nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short-and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state. The observed spectral jumps were statistically analyzed to reveal the dynamics of the molecular environment. The analysis together with MD and QM/MM calculations show that the excited-state planarization of the flapping probe occurs only when sufficiently large polymer free volume of more than, at least, 280 Å 3 is available close to the molecule, and that such free volume lasts for an average of 1.2 s.
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