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An electron pushing group has been introduced to a Schiff-base compound, 2-((2-(quinolin-2-yl)hydrazono)methyl)phenol (HQP) to get another Schiff-base molecule, namely, 4-methyl-2-((2-(quinolin-2-yl)hydrazono)methyl)phenol (HMQP), to modulate the Zn2+ sensing properties of the probe. HQP and HMQP have been synthesized by Schiff-base condensation between 2-hydrazinylquinoline and the respective aldehyde in 1:1 ratio and characterized by standard methods. Both the compounds show their Zn2+ sensing ability but to different extents. The fluorescence intensity of HQP at ~490 nm (λex = 410 nm) increases by about 4.5 folds in the presence of one equivalent of Zn2+ ion. However, the fluorescence intensity is enhanced by around 30 folds in the presence of one equivalent of Zn2+ in case of HMQP. The fluorescence peak of HMQP at 502 nm (λex = 420 nm) is shifted to 515 nm in the presence of Zn2+ whereas same type of shifting for HQP is found to be negligible. Some theoretical calculations have been performed to look into the spectral transitions of HMQP. Fluorescence intensity enhancement is explained by PET mechanism. Limit of detection (LOD) value for HMQP has been determined to be 220.6 nM, showing its good sensitivity towards zinc. The color change of HMQP under visible light is not conclusive in the presence of different metal ions, but only Zn2+ can induce green coloration to HMQP solution under UV light, thus indicating the possibility of naked eye detection by the analyte. HMQP with one equivalent of Zn2+ displays high fluorescence intensity in the pH range of 7.0–9.0 indicating its suitability towards biological applications. The probe has been utilized to live cell imaging studies using C6 cells.

A rhodamine-based compound, 2-(2-((3-(tert-butyl)-2-hydroxybenzylidene)amino)ethyl)-3′-6′-bis(ethylamino)-2′,7′-dimethylspiro[indoline-1,9′-xanthen]-3-one, (HL-t-Bu), is reported here as a dual chemosensor for Zn2+ and Al3+ ions. This compound has been synthesized under mild conditions with high yield and characterized by elemental analysis and different standard spectroscopic methods. Its structure has been confirmed by single-crystal X-ray diffraction analysis. It acts as a fluorescent dual sensor for Zn2+ and Al3+ in 10 mM HEPES buffer in the methanol/water mixture (9:1, pH = 7.4) with well-separated excitation and emission wavelengths. The fluorescence intensity at 457 nm of HL-t-Bu increases by ∼7 folds in the presence of 1 equiv of Zn2+ when it is excited at 370 nm. With the excitation at 500 nm, the emission intensity of the probe at 550 nm increases massively (∼650 times) in the presence of 1 equiv of Al3+. No other metal has any significant effect on the enhancement of the emission intensity of t...

A rhodamine based chemosensor, 3-(((2-(3′,6′-bis(ethylamino)-2′,7′-dimethyl-3-oxospiro[isoindoline-1,9′-xanthen]-2-yl)ethyl)imino)methyl)-2-hydroxy-5-methylbenzaldehyde (HL-CHO), has been developed for the detection of Al3+, Cr3+ and Fe3+ ions. The absorbance of HL-CHO at 528 nm increases significantly in HEPES buffer in methanol : water (9 : 1, v/v) (pH 7.4) in the presence of Al3+, Cr3+ and Fe3+ ions with the alteration of solution color from colorless to pink. The fluorescence intensity of the probe at 550 nm enhances by 1465, 588 and 800 fold in the presence of Al3+, Cr3+ and Fe3+ ions, respectively. To the best of our knowledge, this huge increase in fluorescence intensity with Al3+ and Cr3+ has not been observed for other rhodamine based chemosensing systems. The weak fluorescence and no coloration of the probe are due to the existence of a spirolactam ring. The trivalent cations induce the opening of the spirolactam ring and consequently change the color and the fluorescence intensity followed by the 1 : 1 complex formation with HL-CHO which are evident from Job's analysis, ESI mass spectral analysis and elemental analysis. The quantum yield and lifetime of HL-CHO have increased considerably in the presence of the trivalent cations. The high sensitivity of the probe towards all the cations is evident from the nM order of LOD values. This has been used in living cell imaging studies with the human neuroblastoma SH-SY5Y cell line. Having appended –CHO groups for Schiff-base condensation with other amines, HL-CHO could be a potential precursor for future chemosensors.

We report here 2-((2-morpholinoethylimino)methyl)-4-bromophenol (Hmmbp) as a dual chemosensor for the detection of Zn2+ and H2AsO4− ions in 10 mM HEPES buffer in water: methanol (9: 1, v/v) (pH = 7.4). It has been synthesized by the condensation between 5-bromo-2-hydroxybenzaldehyde and 2-morpholinoethanamine and characterized by different methods. Its fluorescence intensity at 458 nm increases by 32-fold in the presence of one eqv. of Zn2+ (λex:378 nm). Fluorescence enhancement occurs via PET and CHEF mechanism. Other cations cannot induce any considerable change in fluorescence properties of the probe. LOD value for Zn2+ has been determined to be 4.41 × 10−7 M. On the other hand, fluorescence intensity of Hmmbp enhances at 503 nm with one eqv. of H2AsO4− ion (λex:414 nm). In case of anion sensing, restriction of C N isomerization due to hydrogen bonding and ICT mechanism are responsible for the changes of fluorescence of Hmmbp. Detection limit for H2AsO4− has been found to be 3.22 × 10−7 M. The chemosensor is selective for arsenate ion over several common anions. It forms 1:1 complex with both Zn2+ and H2AsO4−.The probe has been utilized to image both the species using C6 rat brain glioma cells.

Proper fusion of fluorescence mechanisms in a single fluorophore unit is highly desirable to obtain better sensitivity, as well as selectivity towards a particular metal ion. In this regard, a Zn2+ chemosensor exhibiting strong fluorescence through synergistic CHEF-PET-ESIPT fluorescence mechanism has not received substantial deployment. This type of chemosensor provides an ample avenue to detect metal ions with a large stokes shift and are useful in living cell imaging study. Herein, we report an unparalleled Zn2+ chemosensor (L) based on these three types of fluorescence mechanisms by condensing 2,6-diformyl-4-methylphenol and 2-hydrazinyl-4,6-dimethylpyrimidine. All the three types of mechanism were experimentally verified by UV-Vis, fluorescence and time resolved photoluminescence (TRPL) spectroscopic evaluation. The sensor L and Zn2+ formed a 1 : 1 ratio complex demonstrating a high binding constant value (Ka = 4.812 × 105 M−1) and L showed clear discrimination from the Cd2+ ion. The limit of detection (LOD) and limit of quantification (LOQ) were calculated to be 9.727 × 10−7 (M) and 3.24 × 10−6 (M), respectively. We have also shown that cell imaging can be performed using L without many cytotoxicity concerns.

2-Formyl-4-methyl-6-(2-benzoimidazolyliminomethyl)phenol (HL1) has been synthesized via Schiff-base condensation between 4-methyl-2,6-diformylphenol and 2-aminobenzimidazole in a 1:1 ratio in acetonitrile and characterized using elemental analysis and different spectroscopic methods. HL1 has been found to be a selective fluorescence sensor for Zn2+ ions. The emission intensity of HL1 at 528 nm in 10 mM HEPES buffer in water:methanol (1:9, v/v) (pH = 7.2) increases in the presence of Zn2+ when it is excited at 445 nm. Other metal ions can induce a slight increment or lowering of emission intensity. The spectral properties of HL1 and 2-formyl-4-methyl-6-(2-benzoimidazolylmethyliminomethyl)phenol (HL2) have been compared. It has been found that the presence of the methylene group in HL2 can have a significant effect on the absorption and fluorescence peak positions of the Schiff-base molecule and its zinc complex. Some theoretical calculations have been done to get a better view into the different spectral transitions. HL1 and HL2 have been found to be highly sensitive towards the detection of Zn2+ ions with very low LOD values. Excitation in the visible region and the effect of pH on the emission intensity of HL1 encourage us to carry out biological studies. HL1 has been used for human lung cancer cell (A549) imaging without cytotoxicity.

The well known rhodamine framework offers an ideal model for the development of fluorescence enhanced chemosensors. Herein, a novel and simple molecule chemosensor, (E)-2-((benzo[d][1,3]dioxol-4-ylmethylene)amino)-3′,6′-bis(diethylamino)spiro[isoindoline-1,9′-xanthen]-3-one ( L ), has been designed by combining a rhodamine B hydrazide and a benzo[d][1,3]dioxole-4-carbaldehyde in a single molecule to prove the selectivity and sensitivity for Al 3+ and Cr 3+ in a dual-channel mode (fluorescence emission and UV–Vis). The signal transduction occurred by the increase of conjugation in the ring-open form than in the ring-closed form. Furthermore, the chemosensor L could also be used as an imaging probe without cytotoxicity for uptake and detection of Al 3+ ion in HeLa cells.

Triazole motif linked rhodamine derivatives 1 and 2 were synthesized. Chemosensor 1 recognizes both Hg2+ and Pb2+ ions in CH3CN–water (4/1, v/v; 10 μM tris HCl buffer, pH 7.0) both colorimetrically and fluorometrically. In addition, chemosensor 1 is cell permeable and detects intercellular Hg2+ and Pb2+ ions. The aqueous phase recognition of these ions was also studied with a resin bound sensor 2 which exhibits more sensitivity and selectivity towards Hg2+ over Pb2+ ion.

A new water-soluble rhodamine-based Al3+ ion-selective probe (L1) was synthesised and characterized by physico-chemico and spectroscopic tools. In the presence of a large excess of other competing ions, L1 specifically binds Al3+ ions with a concurrent visually observable change from colorless to pink in electronic spectral behavior, making it possible to detect the presence of Al3+ ions with the naked eye. The addition of Al3+ ions to a solution of L1 in HEPES buffer (1 mM, pH 7.4, 2% EtOH) at 25 °C, results in a decrease in the weak fluorescence intensity at λem = 470 nm, while a new peak (at λem = 588 nm) increases gradually through a fluorescence resonance energy transfer process. This ratiometric enhancement helps to detect Al3+ ions at a very low concentration of 33 nM. The detection limit of L1 for Al3+ ions was estimated to be 6.19 × 10−9 M using the 3σ method. This probe is also useful for imaging Al3+ ions in HeLa cells.

A new chelating ligand [4-methyl-2,6-bis-(pyridin-2-yl-hydrazonomethyl)-phenol] (1) was prepared by the condensation of 2-hydrazinylpyridine with 2,6-diformyl-p-cresol. Compound 1 exhibits weak fluorescence due to intramolecular photoinduced electron transfer (PET). The sensor (1) demonstrates Zn(2+)-specific emission enhancement due to the “PET off” process through a 1:1 binding mode with the metal ion. The fluorescence quantum yield of chemosensor 1 is only 0.020, and it increases more than 14-fold (0.280) in the presence of one equivalent of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to remain either unchanged or weakened except for Cd(2+). The new sensor showed ‘naked-eye’ detection of Zn(2+) ions: a color change of the solution from colorless to yellow. Ratiometric displacement of Cd(2+) ions from the complex by Zn(2+) ions supports the formation of a more stable sensor–Zn(2+) complex over the sensor–Cd(2+) complex. The experimental findings have been correlated with theoretical results using the B3LYP functional and 6-31G (d, p), LANL2DZ basis set for Cd(2+) (2) and Zn(2+) (3) complexes, respectively, by the Density Functional Theory (DFT) method. Moreover, the ability of probe 1 to sense Zn(2+) within human melanoma cancer cells has been explored, and the Zn(2+)-probing process in living cells was found to be reversible with zinc chelator solution of N,N,N,N-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) or EDTA.

A new highly sensitive and selective Hg(II) probe, 2-(rhodamine-b-hydrazido)-N-(quinolin-8-yl)acetamide (L1) was developed and characterized. L1 specifically binds to Hg(II) in the presence of a large excess of other competing ions with visually observable changes in both electronic and fluorescence spectral behaviour to make possible the naked eye detection of Hg(II) at a very low level (up to 4.5 × 10−7 M) through a fluorescence resonance energy transfer (FRET) process in HEPES buffer (1 mM, pH 7.4; 2% EtOH) at 25 °C. The theoretical and experimental kinetic study also support the binding of Hg(II) ion to induce the opening of the spirolactam ring in L1 for enabling the FRET process. Further studies reveal that the selective dissociation of the L–Hg complex in the presence of sulphide anions to restore the native structure of L1 is also useful in the detection of sulfide anions with a detection limit of a submicromolar range in the same medium of HEPES buffer (1 mM, pH 7.4; 2% EtOH) at 25 °C. L1 could be employed as a FRET based time dependent reversible chemosensor for imaging Hg(II) in living cells and whole bodies, and also could be used as an imaging probe for the detection of sulfide anions in HeLa cells.

A diformyl-p-cresol (DFC)-8-aminoquinoline based dual signaling probe was found to exhibit colorimetric and fluorogenic properties on selective binding towards Mg(2+) and Zn(2+). Turn-on fluorescent enhancements (FE) as high as 40 fold and 53 fold in 9 : 1 MeCN/water (v/v) at pH 7.2 in HEPES buffer for Mg(2+) and Zn(2+), respectively, were observed. The binding constants determined from the fluorescence titration data are: K = (1.52 ± 0.21) × 10(5) M(-1) and (9.34 ± 4.0) × 10(3) M(-2) at n = 1 and 0.5, for Mg(2+) and Zn(2+), respectively. The L : M binding ratios were also determined by Job's method, which support the above findings. This is further substantiated by HRMS analysis. Due to solubility in mixed organo-aqueous solvents as well as cell permeability it could be used for the in vitro/in vivo cell imaging of Mg(2+) and Zn(2+) ions with no or negligible cytotoxicity. This probe could be made selective towards Mg(2+) over Zn(2+) in the presence of TPEN, both under intra- and extracellular conditions and is superior to other Mg(2+) probes which suffer from selectivity of Mg(2+) over Ca(2+) or Zn(2+). Furthermore the dissociation constant (Kd = 6.60 μM) of the Mg(2+)-() complex is far lower than the so far reported Mg(2+) probes which fall in the mM range.

The effect of substituents on FRET in two newly designed rhodamine-based Hg(2+) ion selective chemosensors (L¹ and L²) has been explored by a systematic experimental and theoretical study. Comparison of these sensors in the analytical study and imaging of Hg(2+) ions in living cells has also been included.

An efficient fluorescent Cr3+ receptor, 2-(5,6-dihydro-benzo-[4,5]imidazo[1,2-c]quinazolin-6-yl)-quinolin-8-ol (H2L1) was synthesized and characterized by physico–chemico and spectroscopic tools along with single crystal X-ray crystallography. This probe (H2L1) behaves as a highly selective fluorescent sensor for Cr3+ ions at biological pH in ethanol–water (1 : 5, v/v) HEPES buffer (0.1 M, pH 7.4) at 27 °C. Metal ions, viz. alkali (Na+, K+), alkaline earth (Mg2+, Ca2+), and transition-metal ions ((Mn2+, Fe3+, Co3+, Ni2+, Cu2+, Zn2+) and Pb2+, Ag+ did not interfere. The lowest detection limit for Cr3+ was calculated to be 3.6 × 10−7 mol L−1 within a very short responsive time (15–20 s) in ethanol–water (1 : 5, v/v) HEPES buffer (0.1 M, pH 7.4) at 27 °C. The sensor is efficient for detection of Cr3+ in vitro, developing a good image of the biological organelles.