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A new sensor (L3) based on Rhodamine-B-en (2) and 2-(pyridin-2-ylmethoxy)benzaldehyde (1) has been developed for highly sensitive and selective recognition of NO in purely aqueous medium where the reaction of NO with the fluorophore leads to an unusual formation of nitrosohydroxylamine with the selective opening of the spirolactam ring over different cations, anions, amino-acids and other biological species with prominent enhancement in absorption and emission intensities. A large enhancement of fluorescence intensity for NO (11 fold) was observed upon addition of 3 equivalents of NO into the sensor in aqueous HEPES buffer (20 mM) at pH 7.20, μ = 0.05 M NaCl with naked eye detection. The corresponding Kf value was evaluated to be (7.55 ± 2.04) × 104 M-1 from the fluorescence titration plot. Quantum yields of L3 and the [L3 + NO] compound are found to be 0.07 and 0.77, respectively, using Rhodamine-6G as the standard. The LOD for NO was determined by the 3σ method and found to be 83.4 nM. The L3 sensor has low cytotoxicity, and is cell permeable and suitable for in vitro NO sensing. The in vivo compatibility of the sensor was also checked on zebrafish.

A new, easily synthesizable rhodamine-based chemosensor with potential N2O2 donor atoms, L(3), has been characterized by single-crystal X-ray diffraction together with (1)H NMR and high-resolution mass spectrometry (HRMS) studies. L(3) was found to bind selectively and reversibly to the highly toxic Hg(2+) ion. The binding stoichiometry and formation constant of the sensor toward Hg(2+) were determined by various techniques, including UV-vis, fluorescence, and Job's studies, and substantiated by HRMS methods. None of the biologically relevant and toxic heavy metal ions interfered with the detection of Hg(2+) ion. The limit of detection of Hg(2+)calculated by the 3σ method was 1.62 nM. The biocompatibility of L(3) with respect to its good solubility in mixed organic/aqueous media (MeCN/H2O) and cell permeability with no or negligible cytotoxicity provides good opportunities for in vitro/in vivo cell imaging studies. As the probe is poorly soluble in pure water, an attempt was made to frame nano/microstructures in the absence and in the presence of sodium dodecyl sulfate (SDS) as a soft template, which was found to be very useful in synthesizing morphologically interesting L(3) microcrystals. In pure water, micro-organization of L(3) indeed occurred with block-shaped morphology very similar to that in the presence of SDS as a template. However, when we added Hg(2+) to the solution of L(3) under the above two conditions, the morphologies of the microstructures were slightly different; in the first case, a flowerlike structure was observed, and in second case, a simple well-defined spherical microstructure was obtained. Optical microscopy revealed a dotlike microstructure for L(3)-SDS assemblies, which changed to a panicle microstructure in the presence of Hg(2+). UV-vis absorption and steady-state and time-resolved fluorescence studies were also carried out in the absence and presence of Hg(2+), and also the SDS concentration was varied at fixed concentrations of the receptor and guest. The results revealed that the fluorescence intensity increased steadily with [SDS] until it became saturated at ∼7 mM SDS, indicating that the extent of perturbation to the emissive species increases with the increase in [SDS] until it becomes thermodynamically stable. There was also an increase in anisotropy with increasing SDS concentration, which clearly manifests the restriction of movement of the probe in the presence of SDS.

A new rhodamine 6G-benzylamine-based sensor (L1), having only hydrocarbon skeletons in the extended part, was synthesized and characterized by single-crystal X-ray crystallographic study. It exhibited excellent selective and sensitive recognition of trivalent metal ions M3+ (M = Fe, Al and Cr) over mono- and di-valent and other trivalent metal ions. A large enhancement of the fluorescence intensity for Fe3+ (41-fold), Al3+ (31-fold) and Cr3+ (26-fold) was observed upon the addition of 3.0 equivalent of these metal ions into the probe in H2O/CH3CN (4 : 1, v/v, pH 7.2) with naked eye detection. The corresponding Kf values were evaluated to be 9.4 × 103 M−1 (Fe3+), 1.34 × 104 M−1 (Al3+) and 8.7 × 103 M−1 (Cr3+). Quantum yields of the L1, [L1–Fe3+], [L1–Al3+] and [L1–Cr3+] complexes in H2O/CH3CN (4 : 1, v/v, pH 7.2) were found to be 0.012, 0.489, 0.376 and 0.310, respectively, using rhodamine-6G as standard. LODs for Fe3+, Al3+ and Cr3+ were determined by 3σ methods and found to be 1.28, 1.34 and 2.28 μM, respectively. Cyanide ion scavenged Fe3+ from the [Fe3+–L1] complex and quenched its fluorescence via its ring-closed spirolactam form. Advanced level molecular logic devices using different inputs (2 and 4 inputs) as advanced level logic gates and memory devices were constructed. The large enhancement in fluorescence emission of L1 upon complexation with M3+ metal ions makes the probe suitable for the bio-imaging of M3+ (M = Fe, Al and Cr) in living cells. [ABSTRACT FROM AUTHOR]

A sensor (HL5) based on rhodamine 6G–en and 3-(3,5-dimethyl-pyrazol-1-ylmethyl)-2-hydroxy-5-methyl-benzaldehyde (HL4) has been developed for a highly sensitive and selective CHEF based recognition of trivalent metal ions M3+ (M = Al, Fe and Cr) over mono- and di-valent and other biologically abundant trivalent metal ions with prominent enhancement in absorption and emission intensities. A large enhancement of fluorescence intensities for Fe3+ (21 fold), Al3+ (14 fold) and Cr3+ (10 fold) was observed upon addition of 1.8 equivalents of these metals into the probe in methanol/H2O (1 : 1, v/v, pH 7.2) with the possibility of naked eye detection. The corresponding Kf values were evaluated to be 6.7 × 104 M−1 (Fe3+); 8.2 × 104 M−1 (Al3+) and 6.0 × 104 M−1 (Cr3+). The quantum yields of HL5 and [HL5–Fe3+] and [HL5–Cr3+] and [HL5–Al3+] complexes in methanol/H2O (1 : 1, v/v, pH 7.2) are found to be 0.013, 0.290, 0.120, and 0.158, respectively, using rhodamine-6G as the standard. The LOD for Fe3+, Al3+ and Cr3+ were determined by 3σ methods with values 0.29, 0.34 and 0.31 μM, respectively. An arsenate ion snatches Al from the Al–HL5 complex and quenches its fluorescence via its ring closed spirolactam form. Advanced level molecular logic devices using the inputs 2 and 4 and memory devices, have been constructed. The low cytotoxicity and large enhancement in fluorescence intensity of HL5 upon complexation with M3+ metal ions make the probe suitable for bio-imaging of M3+ (M = Al, Fe and Cr) in living cells and native cellular iron pools. [ABSTRACT FROM AUTHOR]