Efficient solid- and solution-state emissive reusable solvatochromic fluorophores for colorimetric and fluorometric detection of CN.

In this work, a novel organic receptor, CPI [(E)-3-(4-(9H-carbazol-9-yl)phenyl)-2-(1H-benzo[d]imidazol-2-yl)acrylonitrile], was rationally designed and successfully fabricated for selective and sole recognition of CN- ions over other competitive anions through an obvious chromogenic and ratiometric emission change in DMSO. The distinct and prominent color change upon the addition of CN- can be attributed to the typical ICT process, which is induced by the deprotonation of acidic NH protons in the imidazole moiety. The sensor displayed strong solvatochromic effects in commonly used organic solvents such as n-hexane, toluene, diethyl ether, DCM, THF, DMF and DMSO. The chemical structure of the sensor was characterized by single-crystal X-ray diffraction, 1HNMR, 13CNMR, IR and mass spectroscopy. Significantly, the probe can function as a fluorescence-based sensor for the efficient detection of low-level water in organic solvents. The solid-state emission properties of CPI were successfully applied to recognise cyanide in a solid-state platform with naked eye-visualized distinct color change. The probe can be made reusable by adding TFA into the CN- treated probe solution. The detection limit of CPI towards CN- was determined to be 4.48 × 10-8 M. More importantly, the sensor is capable of detecting CN- in food samples and has been employed for wastewater treatment. Besides, easy-to-prepare CPI-coated test strips provide a simple, reusable and easy-to-handle protocol for the qualitative identification of CN- conveniently. Finally, density functional theory and time-dependent density functional theory were performed to verify the experimental outcomes theoretically.

Fabrication of a New Coumarin Based Fluorescent "turn-on" Probe for Distinct and Sequential Recognition of Al3+ and F- Along With Its Application in Live Cell Imaging.

A new coumarin based fluorescent switch PCEH is fabricated which displays high selective sensing towards Al3+ among other metal cations at physiological pH. On gradual addition of Al3+, PCEH shows a brilliant "turn-on" emission enhancement in MeOH/H2O (4/1, v/v) solution. This new fluorescent switch is proven to be a reversible probe by gradual addition of F- into the PCEH-Al3+ solution. Detection limit as well as binding constant values are calculated to be in the order of 10-9 M and 104 M-1 respectively. We have also explored its potential as a biomarker in the application of live cell imaging using breast cancer cells (MDA-MB-231 cell).

A new ratiometric switch "two-way" detects hydrazine and hypochlorite via a "dye-release" mechanism with a PBMC bioimaging study.

A new ratiometric fluorescent probe (E)-2-(benzo[d]thiazol-2-yl)-3-(8-methoxyquinolin-2-yl)acrylonitrile (HQCN) was synthesised by the perfect blending of quinoline and a 2-benzothiazoleacetonitrile unit. In a mixed aqueous solution, HQCN reacts with hydrazine (N2H4) to give a new product 2-(hydrazonomethyl)-8-methoxyquinoline along with the liberation of the 2-benzothiazoleacetonitrile moiety. In contrast, the reaction of hypochlorite ions (OCl-) with the probe gives 8-methoxyquinoline-2-carbaldehyde. In both cases, the chemodosimetric approaches of hydrazine and hypochlorite selectively occur at the olefinic carbon but give two different products with two different outputs, as observed from the fluorescence study exhibiting signals at 455 nm and 500 nm for hydrazine and hypochlorite, respectively. A UV-vis spectroscopy study also depicts a distinct change in the spectrum of HQCN in the presence of hydrazine and hypochlorite. The hydrazinolysis of HQCN exhibits a prominent chromogenic as well as ratiometric fluorescence change with a 165 nm left-shift in the fluorescence spectrum. Similarly, the probe in hand (HQCN) can selectively detect hypochlorite in a ratiometric manner with a shift of 120 nm, as observed from the fluorescence emission spectra. HQCN can detect hydrazine and OCl- as low as 2.25 × 10-8 M and 3.46 × 10-8 M, respectively, as evaluated from the fluorescence experiments again. The excited state behaviour of the probe HQCN and the chemodosimetric products with hydrazine and hypochlorite are studied by the nanosecond time-resolved fluorescence technique. Computational studies (DFT and TDDFT) with the probe and the hydrazine and hypochlorite products were also performed. The observations made in the fluorescence imaging studies with human blood cells manifest that HQCN can be employed to monitor hydrazine and OCl- in human peripheral blood mononuclear cells (PBMCs). It is indeed a rare case that the single probe HQCN is found to be successfully able to detect hydrazine and hypochlorite in PBMCs, with two different outputs.

A fluorescent "ON-OFF-ON" switch for the selective and sequential detection of Hg2+ and I- with applications in imaging using human AGS gastric cancer cells.

A new fluorescent "on-off-on" probe (BIPQ) is designed and developed which selectively binds with Hg2+; its emission intensity is quenched almost 40-fold at 455 nm without interference from other metal cations. On gradual addition of I- to the solution of BIPQ-Hg2+, the emission reverts to its original intensity. The limits of detection of BIPQ for Hg2+ and I- are found to be on the order of 3.12 × 10-9 and 5.48 × 10-8 M, respectively, which shows clearly that BIPQ can sense Hg2+ at a very minute level. DFT and TDDFT studies are conducted with the probe to establish similarity between theoretical and experimental outcomes. Finally, to demonstrate its practical benefit in biological fields, live cell imaging experiments with BIPQ are carried out to detect Hg2+ in human AGS gastric cancer cell lines.

An Efficient Fluorescence "Turn-On" Chemosensor Comprising of Coumarin and Rhodamine Moieties for Al3+ and Hg2.

A potent fluorescence 'turn-on' receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg2+ and Al3+ is synthesized by condensation of rhodamine 6G hydrazide and 4-hydroxy-3-acetylcoumarin. In presence of Al3+ and/or Hg2+ the receptor (HL) exhibits deep pink colouration and a sharp band at 528 nm is appeared in UV-vis titration. Upon gradual addition of Al3+ and/or Hg2+ to the solution of HL significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H2O (1:5, v/v) medium. The receptor is strongly bound to Al3+ and/or Hg2+ and the association constants (Ka) are found to be 1.74 × 104 and 1.04 × 104 M- 1 for Al3+ and Hg2+ respectively. Graphical Abstract A potent fluorescence 'turn-on' receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg2+ and Al3+ is synthesized and characterized. In presence of Al3+ and/or Hg2+ the receptor (HL) exhibits deep pink colouration and significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H2O (1:5, v/v) medium. The receptor is strongly bound to Al3+ and/or Hg2+ and the association constants (Ka) are found to be 1.74 × 104 and 1.04 × 104 M- 1 for Al3+ and Hg2+ respectively.

A Phenanthraquinone Based Fluorescent Probe for Sequential Detection of Cu2+ and SO32.

Herein we report the selective detection of Cu2+ and SO32- by phenanthraquinone thiosemicarbazone (PQTSC) chemosensor. The chemosensor is efficient in detecting Cu2+ over other metal ions, while the PQTSC-Cu2+ complex selectively sense SO32- over other anions. On addition of Cu2+ to the receptor solution, quenching of emission intensity is observed by 16 folds and upon gradual addition of SO32- to this solution, the emission intensity increases and the maxima is regained. The limit of detection for Cu2+ detection calculated from fluorescence titration is 1.06 × 10-8 M and the association constant of PQTSC with Cu2+ is found to be 2.18 × 105.

Novel pyridyl based azo-derivative for the selective and colorimetric detection of nickel(II).

A highly sensitive and selective pyridyl based colorimetric chemosensor (H2L) for the efficient detection of Ni(2+) has been reported. The synthesized chemosensor H2L is highly efficient in detecting Ni(2+) even in the presence of other metal ions that commonly co-exist with Ni(2+). H2L also shows distinct color change from green to deep red visible under naked eye due to specific binding with Ni(2+). This color change is due to formation of a new band at 510 nm upon gradual addition of Ni(2+). The association constant has been found to be 1.27×10(5) M(-1) with limit of detection (LOD) of 8.3×10(-7) M. Electronic structure of the H2L-Ni(2+) complex and sensing mechanism have been interpreted theoretically by DFT and TDDFT calculations.