Subarna Guha

Thiophene anchored coumarin derivative as a turn-on fluorescent probe for Cr3+: cell imaging and speciation studies.

A thiophene-coumarin hybrid molecule, (6E)-6-((thiophen-2-yl)methyleneamino)-2H-chromen-2-one (TMC) has been prepared and its single crystal X-ray structure is reported. TMC can selectively detect Cr(3+) in presence of other common cations. Both TMC and its Cr(3+) complex are well characterized by different spectroscopic techniques like (1)H NMR, QTOF-MS ES(+), FTIR and elemental analysis as well. TMC exhibits fluorescence enhancement upon binding Cr(3+) in CH(3)CN-HEPES buffer (0.02 M, pH 7.4) (4:6, v/v) medium. Detection limit of the method is 1 × 10(-6)M. Binding constant is estimated with the Benesi-Hildebrand method and the value 8 × 10(4) indicates a fairly strong interaction between TMC and Cr(3+). Speciation studies have been performed in a fast and environment friendly way using least sample volume, less hazardous chemicals and solvents. Cr(3+) assisted restricted rotation around the imine bond and inhibited photo-induced electron transfer from the N,S-donor sites to the coumarin unit are responsible for fluorescence enhancement. TMC is capable to detect intracellular Cr(3+) in living cells.

Nickel(II)-induced excimer formation of a naphthalene-based fluorescent probe for living cell imaging.

Ni(2+)-induced intramolecular excimer formation of a naphthalene-based novel fluorescent probe, 1-[(naphthalen-3-yl)methylthio]-2-[(naphthalen-6-yl)methylthio]ethane (L), has been investigated for the first time and nicely demonstrated by excitation spectra, a fluorescence lifetime experiment, and (1)H NMR titration. The addition of Ni(2+) to a solution of L (DMSO:water = 1:1, v/v; λ(em) = 345 nm, λ(ex) = 280 nm) quenched its monomer emission, with subsequent enhancement of the excimer intensity (at 430 nm) with an isoemissive point at 381 nm. The fluorescence lifetime of free L (0.3912 ns) is much lower than that of the nickel(2+) complex (1.1329 ns). L could detect Ni(2+) as low as 1 × 10(-6) M with a fairly strong binding constant, 2.0 × 10(4) M(-1). Ni(2+)-contaminated living cells of plant origin could be imaged using a fluorescence microscope.

An Al3+ induced green luminescent fluorescent probe for cell imaging and naked eye detection

A novel pyrimidine based Al3+ selective fluorescent probe (L) has been synthesised by a facile one step coupling of 4,5-diamino pyrimidine with 2-hydroxy naphthaldehyde. L has been obtained in pure crystalline form without any column chromatographic purification. Upon binding Al3+, the single emission band of L undergoes red shift from 470 nm to dual emission peaks viz. 505 nm and 538 nm with appearance of a very intense green luminescence. L could detect as low as 2.9 × 10−7 M Al3+ with a binding constant value of 5.4 × 104 M−1. Al3+ contaminated cells became green in the presence of L making it suitable for intracellular Al3+ detection.

9-Acridone-4-carboxylic acid as an efficient Cr(III) fluorescent sensor: Trace level detection, estimation and speciation studies

9-Acridone-4-carboxylic acid has been established as an efficient Cr(III) fluorescent sensor. The binding of this ligand with Cr(III) is confirmed by FTIR, thermal and mass spectral analysis of the product. Based on this chelation assisted fluorescence quenching, a highly sensitive spectrofluorometric method is developed for trace level detection, estimation and speciation studies of chromium in DMF-water. The ligand has an excitation and emission maxima at 408 nm and 498.4 nm, respectively. The equilibrium binding constant of the ligand with Cr(III) is 8.1378 × 10(4) as calculated using Stern-Volmer equation. Up to 9 × 10(-6)mol L(-1) of [Cr(3+)], linearity has been observed. The interference of foreign ions has been found to be negligible.

Methionine–pyrene hybrid based fluorescent probe for trace level detection and estimation of Hg(II) in aqueous environmental samples: Experimental and computational studies

A new fluorescent, Hg(2+) selective chemosensor, 4-methylsulfanyl-2-[(pyren-4-ylmethylene)-amino] butyric acid methyl ester (L, MP) was synthesized by blending methionine with pyrene. It was well characterized by different analytical techniques, viz. (1)H NMR, (13)C NMR, QTOF mass spectra, elemental analysis, FTIR and UV-vis spectroscopy. The reaction of this ligand with Hg(2+) was studied by steady state and time-resolved fluorescence spectroscopy. The Hg(2+) complexation process was confirmed by comparing FTIR, UV-vis, thermal, QTOF mass spectra and (1)H NMR data of the product with that of the free ligand values. The composition (Hg(2+):L=1:1) of the Hg(2+) complex in solution was evaluated by fluorescence titration method. Based on the chelation assisted fluorescence quenching, a highly sensitive spectrofluorometric method was developed for the determination of trace amounts of Hg(2+) in water. The ligand had an excitation and emission maxima at 360 nm and 455 nm, respectively. The fluorescence life times of the ligand and its Hg(2+) complex were 1.54 ns and 0.72 ns respectively. The binding constant of the ligand, L with Hg(2+) was calculated using Benesi-Hildebrand equation and was found to be 7.5630×10(4). The linear range of the method was from 0 to 16 μg L(-1) with a detection limit of 0.056 μg L(-1) for Hg(2+). The quantum yields of the ligand and its Hg(2+) complex were found to be 0.1206 and 0.0757 respectively. Both the ligand and its Hg(2+) complex have been studied computationally (Ab-initio, Hartree Fock method) to get their optimized structure and other related physical parameters, including bond lengths, bond angles, dipole moments, orbital interactions etc. The binding sites of the ligand to the Hg(2+) ion as obtained from the theoretical calculations were well supported by (1)H NMR titration. The interference of foreign ions was negligible. This method has been successfully applied to the determination of mercury(II) in industrial waste water.

Thiophene anchored naphthalene derivative: Cr3+ selective turn-on fluorescent probe for living cell imaging

A naphthalene-based thiophene derivative (L) can act as a Cr3+ selective turn-on fluorescence probe in aqueous methanol. The structure of L has been established from different spectroscopic data and confirmed by X-ray crystallography. Under optimum conditions, the fluorescence intensity of L increases linearly from 1.0 × 10−6 to 52 × 10−6 M Cr3+ with a detection limit of 1.5 × 10−7 M. L also exhibits good cell permeability and can detect intracellular Cr3+ in contaminated living cells.

Vanillin-coumarin hybrid molecule as an efficient fluorescent probe for trace level determination of Hg(II) and its application in cell imaging

An efficient Hg(2+) selective fluorescent probe (vanillin azo coumarin, VAC) was synthesized by blending vanillin with coumarin. VAC and its Hg(2+) complex were well characterized by different spectroscopic techniques like (1)H NMR, QTOF-MS ES(+), FTIR and elemental analysis as well. VAC could detect up to 1.25 μM Hg(2+) in aqueous methanol solution through fluorescence enhancement. The method was linear up to 16 μM of Hg(2+). Negative interferences from Cu(2+), Ni(2+), Fe(3+), and Zn(2+) were eliminated using EDTA as a masking agent. VAC showed a strong binding to Hg(2+) ion as evident from its binding constant value (2.2×10(5)), estimated using Benesi-Hildebrand equation. Mercuration assisted restricted rotation of the vanillin moiety and inhibited photoinduced electron transfer from the O, N-donor sites to the coumarin unit are responsible for the enhancement of fluorescence upon mercuration of VAC. VAC was used for imaging the accumulation of Hg(2+) ions in Candida albicans cells.

Anthracene appended coumarin derivative as a Cr(III) selective turn-on fluorescent probe for living cell imaging: a green approach towards speciation studies

A facile one step reaction between 6-aminocoumarin and anthracene-9-carboxaldehyde has resulted in a novel fluorescent probe, 6-((anthracen-9-yl) methyleneamino)-2H-chromen-2-one (AC) which is capable of selectively detecting intracellular Cr3+ in contaminated living cells under a fluorescence microscope. The binding of AC with Cr3+ is well characterized by different spectroscopic techniques. The binding constant values in CH3CN–water (9 : 1, v/v) and methanol–water (9 : 1, v/v) solutions have been estimated to be 1.1 × 105 and 3.1 × 105 respectively using the Benesi–Hildebrand equation. The detection limit for Cr3+ is 0.5 × 10−6 M. The developed method has been used for speciation studies in a fast and environment friendly way using least amounts of samples, non-hazardous chemicals and solvents.

Crystal Structure and Interaction of 6-Amino Coumarin with Nitrite Ion for Its Selective Fluorescence Detection

ABSTRACT 6-Amino coumarin has been established as an efficient nitrite ion selective fluorescent sensor. The developed method shows linearity up to 1.6 × 10−6 mol L−1 of nitrite ion concentration. Interference from other common anions is almost negligible. The reagent shows strong binding affinity towards nitrite ion as evident from its binding constant value (5.8 × 104), estimated by Stern-Volmer method. Some real samples were analyzed. Single crystal X-ray structure of the reagent is reported. Preliminary computational studies on the molecular level interaction between the reagent and nitrite ion were performed by density functional theory (DFT, B3LYP) method.

Spectroscopic Studies of a New Multi-Element Sensitive Fluorescent Probe Derived from 2-(2-pyridyl)benzimidazole: Selective Discrimination of Zn2+ from Its Congeners

ABSTRACT A new multielement sensitive fluorescent probe, 1-(2-(phenylthio)ethyl)-2-(pyridin-2-yl)-1H-benzo[d]imidazole (L), has been synthesized by the reaction between 2-(pyridyl) benzimidazole and 2-chloroethyl phenyl sulfide. Excitation and emission wavelength of L are at 330 and 371 nm, respectively. Among various transition and nontransition metal ions, it can selectively read Zn2+ ion as the emission wavelength of L undergoes a red shift by 31 nm upon binding with Zn2+ in methanol. In the presence of Cd2+, Hg2+, and other common cations, the emission wavelength of L remains unchanged, and thus allows us to discriminate Zn2+ from its congeners. Both L and its Zn2+ complex are well characterized by different spectroscopic techniques like 1H-NMR, ESI-TOF (+) mass, FT-IR, and elemental analysis data. The binding constant value of the complexation reaction between L and Zn2+ is found as 724.6 M−1 in methanol. Density functional theoretical (DFT) studies nicely demonstrate the red shift in the emission wavelength of L upon binding with Zn2+.