Correction: A highly sensitive triazole-based perfectly water soluble novel bis-Schiff base reversible fluorescent-colorimetric chemosensor for fast detection of Pb2+ ions.

[This corrects the article DOI: 10.1039/D3RA06185J.].

A highly sensitive triazole-based perfectly water soluble novel bis-Schiff base reversible fluorescent-colorimetric chemosensor for fast detection of Pb2+ ions.

A reversible fluorescent-colorimetric azino bis-Schiff base receptor for the detection of Pb2+ in aqueous medium has been developed for the first time. Receptor L exhibits an excellent selective and rapid fluorescent-colorimetric response towards Pb2+. The sensitivity of the fluorescent-based assay (0.53 nM) and colorimetric assay (1.0 nM) for Pb2+ is sufficiently good in comparison to previously reported literature. From 1H NMR data, Job plot measurement and the ESI-MS spectrum, a 1 : 2 stoichiometric complexation between L and Pb2+ has been established. Receptor L shows a remarkable detection ability in a wide pH range of 4-8 and it has been successfully utilised in the determination of Pb2+ in aqueous solution of bovine serum albumin protein and in real samples. The geometry of L has been optimized by both DFT studies and NMR, FTIR and mass spectra. Moreover, we have studied molecular docking of the probe L.

Synthesis, Crystal Structure, DFT and Fluorescence Quenching Study of Novel syringe aldehyde-derived hydrazinyl-imidazole Based Schiff base Chemosensor.

In this study, we report a new syringe aldehyde-derived hydrazinyl-imidazole based fluorescent sensor (L) for sensitive detection of different inorganic quenchers (halide ions, bicarbonate ion, sulphide ion and transition metal ions). The chromophore (L) was obtained in good yield by the 1:1 condensation reaction of 2-hydrazino-4,5-dihydroimidazole hydrobromide and 4-hydroxy-3,5-dimethoxy benzaldehyde. L exhibited strong fluorescence in the visible region (around 380 nm) and its interaction with different quenchers was studied in details via fluorescence technique. For the halide ions series, its sensitivity is higher for NaF (Climit = 4 × 10- 4 M) than for NaCl while the fluorescence quenching occurred mainly through a dynamic process. Similar considerations were observed for HCO3- and S2- quencher too, when static and dynamic quenching take place simultaneously. Regarding transition metal ions, at a fixed ion concentration (4 × 10- 6 M), best performance was achieved for Cu2+ and Fe2+ (fluorescence intensity was reduced by 79% and 84.9% respectively), while for other metal ions, the sensor performance was evaluated and found to be very less (< 40%). Thus, minimum detection limits (10- 6 - 10- 5 M range) recommended the use of such derivatives as highly sensitive sensors capable to monitor delicate changes in varied environments.

Organelle-targeting ratiometric fluorescent probes: design principles, detection mechanisms, bio-applications, and challenges.

Biological species, including reactive oxygen species (ROS), reactive sulfur species (RSS), reactive nitrogen species (RNS), F-, Pd2+, Cu2+, Hg2+, and others, are crucial for the healthy functioning of cells in living organisms. However, their aberrant concentration can result in various serious diseases. Therefore, it is essential to monitor biological species in cellular organelles such as the cell membrane, mitochondria, lysosome, endoplasmic reticulum, Golgi apparatus, and nucleus. Among various fluorescent probes for species detection within the organelles, ratiometric fluorescent probes have drawn special attention as a potential way to get beyond the drawbacks of intensity-based probes. This method depends on measuring the intensity change of two emission bands (caused by an analyte), which produces an efficient internal referencing that increases the detection's sensitivity. This review article discusses the literature publications (from 2015 to 2022) on organelle-targeting ratiometric fluorescent probes, the general strategies, the detecting mechanisms, the broad scope, and the challenges currently faced by fluorescent probes.

A quinazolin-based Schiff-base chemosensor for colorimetric detection of Ni2+ and Zn2+ ions and 'turn-on' fluorometric detection of Zn2+ ion.

Herein, we have reported a novel quinazolin-based Schiff base chemosensor (E)-2-benzamido-N'-(1-(pyridin-2-yl)ethylidene)benzohydrazide (L). L has been designed, synthesised and characterised by 1H-NMR, IR spectroscopy, ESI-MS spectrometry and theoretical studies. The receptor showed appreciable colorimetric λ max shift for both Ni2+ and Zn2+ ions and fluorometric "turn on" response in presence of only Zn2+ ion. The Jobs plot analysis revealed that receptor forms 2 : 1 complex with both the ions Ni2+ and Zn2+, further confirmed by ESI-MS analysis. The single crystal structure of L-Ni2+ complex (1) has also been determined. The colorimetric detection limits were calculated to 7.9 nM and 7.5 nM respectively for Ni2+ and Zn2+ in methanol-Tris-HCl buffer medium (10 mM, pH 7.2, 1 : 1 v/v). The chemosensor L can be applied for the recovery of contaminated water samples.

Smartphone coupled with paper-based chemical sensor for on-site determination of iron(III) in environmental and biological samples.

We report a smartphone-paper-based sensor impregnated with cetyltrimethylammonium bromide modified silver nanoparticles (AgNPs/CTAB) for determination of Fe3+ in water and blood plasma samples. The methodology for determination of Fe3+ is based on the change in signal intensity of AgNPs/CTAB fabricated on a paper substrate after the deposition of analyte, using a smartphone followed by processing with ImageJ software. The mechanism of sensing for detection and determination of Fe3+ is based on the discoloration of AgNPs which impregnated the paper substrate. The discoloration is attributed to the electron transfer reaction taking place on the surface of NPs in the presence of CTAB. Fe3+ was determined when the paper was impregnated with 1 mM AgNPs for 5 min of reaction time and the substrate was kept under acidic conditions. The linear range for determination of total iron in terms of Fe3+ was 50-900 µg L-1 with a limit of determination (LOD) of 20 µg L-1 and coefficient of variation (CV) of 3.2%. The good relative recovery of 91.3-95.0% and interference studies showed the selectivity of the method for determination of total iron in water and blood plasma samples. Smartphone-paper-based sensors have advantages of simplicity, rapidity, user-friendliness, low cost, and miniaturization of the method for on-site determination of total iron compared to methods that require sophisticated analytical instruments. Graphical abstract Smartphone-paper-based sensor with cetyltrimethylammonium bromide modified silver nanoparticles for determination of Fe3+ in water and blood plasma samples.

A novel dihydro phenylquinazolinone-based two-in-one colourimetric chemosensor for nickel(ii), copper(ii) and its copper complex for the fluorescent colourimetric nanomolar detection of the cyanide anion.

Currently, considerable efforts have been devoted to the detection and quantification of hazardous multi-analytes using a single probe. Herein, we have developed a simple, environment-friendly colourimetric sensor for the sensitive, selective and rapid detection of Ni2+ and Cu2+ ions using a simple organic Schiff base ligand L in methanol-Tris-HCl buffer (1 : 1 v/v, 10 mM, pH = 7.2). The probe L exhibited a binding-induced colour change from colourless to yellow and fluorescence quenching in the presence of both Ni2+ and Cu2+ ions. The interactions between L and the respective metal ions were studied by Job's plot, electrospray ionisation-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FT-IR), density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The limit of detection (LOD) of L towards Ni2+ and Cu2+ was calculated to be 7.4 × 10-7 M and 4.9 × 10-7 M, respectively. Furthermore, the L-Cu2+ complex could be used as a new cascade fluorescent-colourimetric sensor to detect CN- ions with a very low level of detection (40 nM). Additionally, L could operate in a wide pH range, and thus was successfully applied for the detection and quantification of Ni2+ and Cu2+ in environmental samples, and for building OR- and IMPLICATION-type logic gates.

Mono- and dinuclear manganese(III) complexes showing efficient catechol oxidase activity: syntheses, characterization and spectroscopic studies.

Four side-off compartmental ligands L1-L4 [L1 = N,N'-ethylenebis(3-formyl-5-methyl-salicylaldimine), L2 = N,N'-1-methylethylenebis(3-formyl-5-methylsalicylaldimine), L3 = N,N'-1,1-dimethylethylenebis(3-formyl-5-methylsalicylaldimine) and L4= N,N'-cyclohexenebis(3-formyl-5-methylsalicylaldimine)] having two binding sites, N2O2 and O4, have been chosen to synthesize mononuclear and dinuclear manganese(III) complexes with the aim to study their catecholase activity using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate in the presence of molecular oxygen. In all cases only mononuclear manganese complexes (1-4) were obtained, with manganese coordination taking place at the N2O2 binding site only, irrespective of the amount of manganese salt used. All these complexes have been characterized by routine physico-chemical techniques. Complex MnL2Cl.4H2O (2) has further been structurally characterized by X-ray single crystal structure analysis. Four dinuclear manganese complexes, 5-8, were obtained after condensing the two pending formyl groups on each ligand (L1-L4) with aniline followed by reaction with MnCl2 to put the second Mn atom onto another N2O2 site. The catalytic activity of all complexes 1-8 has been investigated following the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) with molecular oxygen in two different solvents, methanol and acetonitrile. The study reveals that the catalytic activity is influenced by the solvent and to a significant extent by the backbone of the diamine and the behavior seems to be related mainly to steric rather than electronic factors. Experimental data suggest that a correlation, the lower the E(1/2) value the higher the catalytic activity, can be drawn between E(1/2) and Vmax of the complexes in a particular solvent. The EPR measurements suggest that the catalytic property of the complexes is related to the metal center(s) participation rather than to a radical mechanism.

Octahedral monodithiolene complexes of iron: characterization of S,S'-coordinated dithiolate(1-) pi radical monoanions: a spectroscopic and density functional theoretical investigation.

The reaction of cis-[Fe(III)(cyclam)Cl(2)]Cl with 1 equiv of sodium N-diethyldithiocarbamate, toluene-3,4-dithiolate, and maleonitriledithiolate in methanol in the presence of triethylamine afforded the cations [Fe(III)(cyclam)(Et(2)dtc)](2+) (1), [Fe(III)(cyclam)(tdt)](+) (2), and [Fe(III)(cyclam)(mnt)](+) (3), which were isolated as triflate, hexafluorophosphate, and tetrafluoroborate salt, respectively, using sodium triflate, potassium hexafluorophosphate, or sodium tetrafluoroborate as the source for the counteranion. Complexes 1, 2, and 3 possess an S = (1)/(2) ground state (low-spin ferric d(5)). These salts were characterized by X-ray crystallography, UV-vis, Mössbauer, and electron paramagnetic resonance spectroscopies. Cyclic voltammetry revealed that 2 and 3 are reversibly one-electron-reduced, generating neutral 2(red) and 3(red), respectively, and one-electron-oxidized, generating dicationic 2(ox) and 3(ox), respectively. Fe and S K-edge X-ray absorption spectroscopy (XAS) revealed that 2 (S = (1)/(2)) and 2(ox) (S = 0) possess a low-spin ferric ion. Complexes 2 and 3 are S,S'-coordinated to a closed-shell dithiolate(2-) ligand, whereas 2(ox) and 3(ox) consist of a low-spin ferric ion antiferromagnetically coupled to a dithiolate(1-) pi radical ligand. They are singlet diradicals [Fe(III)(cyclam)(dithiolate(*))](2+). The analysis of the sulfur K pre-edge transitions reveals significant multiplet effects in the spectra of 2 and 2(ox), which provide rare experimental evidence for a singlet diradical description for 2(ox). Mössbauer spectroscopy on frozen solutions of 2(red) clearly show the presence of a high-spin ferrous ion (S = 2). The experimentally established electronic structures of the three members of the electron transfer series [Fe(cyclam)(dithiolate)](2+,+,0) have been verified by broken symmetry density functional theoretical calculations, which have been calibrated against the experiment by calculating XAS and Mössbauer spectra.

N,N'-Bis(4-pyridylmethyl-ene)octane-1,8-diamine.

The complete molecule of the title compound, C(20)H(26)N(4), is generated by a crystallographic centre of inversion and the central eight-carbon chain adopts a fully extended conformation. In the crystal, the molecules pack in layers parallel to (010).

Benzil bis-(ketazine).

THE TITLE COMPOUND (SYSTEMATIC NAME: 1,1',2,2'-tetra-phenyl-2,2'-azinodiethanone), C(28)H(20)N(2)O(2), was obtained by the reaction of benzil monohydrazone with chromium(III) nitrate. The dibenzyl-idene hydrazine unit is nearly planar (r.m.s. deviation = 0.073 Å) and the two benzoyl units are oriented almost perpendicular to it [dihedral angle = 87.81 (2), 87.81 (2)°]. The mol-ecules are linked into chains along the c axis by C-H⋯O hydrogen bonds and the chains are cross-linked via C-H⋯π inter-actions involving the benzoyl phenyl rings.

1,2-Diphenyl-2-[4-(4-pyridyl)benzyl-idene-hydrazono]ethan-1-one.

In the title compound, C(26)H(19)N(3)O, the dimethyl-ene hydrazine (-C=N-N=C-) unit is approximately planar, the torsion angle around the N-N bond being 162.2 (6)°. The phenyl and benzoyl-phenyl rings at one end of the hydrazine unit are aligned at angles of 9.5 (5) and 88.5 (4)°, respectively, with respect to the hydrazine unit, whereas the benzene ring at the other end is twisted by an angle of 14.4 (4)°. In the crystal structure, mol-ecules are linked into centrosymmetric dimers by inter-molecular C-H⋯O hydrogen bonds. The monoclinic crystal under investigation shows pseudo-merohedral twinning with twin fractions of 0.63 and 0.37.

Crystal engineering of metalloporphyrin assemblies. New supramolecular architectures mediated by bipyridyl ligands.

Targeted synthesis of new supramolecular motifs of metalloporphyrins in crystals by a concerted mechanism of molecular recognition in three dimensions, aided by organic ligands, is presented; it involves induced assembly of [tetrakis(4-hydroxyphenyl)porphyrinato]zinc species by a combination of axial coordination through bridging bipyridyls and of lateral hydrogen bonding.

Hydrogen-bonded supramolecular lattice of the 1:3:4 complex between [5,10,15,20-meso-tetrakis(4-hydroxyphenyl)porphyrinato-kappa(4)N]zinc(II), dibenzo-24-crown-8 and methanol.

The title compound, [5,10,15,20-meso-tetrakis(4-hydroxyphenyl)porphyrinato-kappa(4)N]zinc(II) tris(dibenzo-24-crown-8) methanol tetrasolvate, [Zn(C(44)H(28)N(4)O(4))].3C(24)H(32)O(8).4CH(4)O, was synthesized and its molecular structure precisely characterized by low-temperature single-crystal analysis. All the components are involved in hydrogen bonding with each other, thus forming an extensively hydrogen-bonded supramolecular lattice. The functionalized porphyrin moiety coordinates both equatorially and axially to the neighboring species.