Nitroquinolone Fused Salicyl and Naphthyl Hydrazone Fluorescent Probes for the Detection of Fe3+and Pb2+ Ions.

The application of quinolones stretches over a large umbrella of medicinal field as well as chemosensor due to the presence of privileged heterocyclic aromatic rig system. Salicyl and Naphthyl Hydrazide motifs are also established fluorophore groups. Therefore in this work, we have designed and synthesized Salicyl hydrazide (3a-c) and naphthyl hydrazide fused nitroquinolones (5a-c) investigated for their fluorescent behaviour. Preliminary UV- absorption studies were carried out and the metal selectivity were examined with various metal ion. Among them, it was found that compound 3a was selective towards Fe3+ ions (λex = 330 nm, 1:1 DMF:H2O at pH = 7.4 in HEPES Buffer medium). 3a shows decrease emission intensity in presence of Fe3+ ions. Compound 5a shows enhancement in fluorescence intensity upon addition of Pb2+ ion (λex = 280 nm, 1:1 DMF:H2O at pH = 7.4 in HEPES Buffer medium). Further, the concentration dependence, competitive binding and EDTA reversibility were studied for selected compounds towards the respective cations selectivity. Jobs plot analysis indicate that 1:1 binding of 3a with Fe3+ ion (Ka = 3.17 x104M-1 and Limit Of Detection (LOD) = 5.1 × 10-7 M) whereas 5a showed 1:2 binding mode with Pb2+ ions (Ka = 2.14 × 106 M-1 and Limit Of Detection (LOD) = 2.613 × 10-9 M). Density Function Theoretical studies were performed as support for the experimental results.

Azine Based Oligoesteric Chemosensors for Cu2+ Ion Detection: Synthesis, Structural Characterization, and Theoretical Investigations.

Synthesized monomer and its three oligoesters were characterized by techniques such as 1H, 13C{1H}, IR, UV, GPC and applied to chemosensor applications. A series of metal ions was studied with fluorophores to evaluate the sensitivity towards Cu2+ ion. The fluorophores results exhibit the selective and sensitive "Turn off" fluorescence response with Cu2+ ion in DMF/H2O (1:1, pH: 7.4, fluorophore: 5 µM) solution. Binding stoichiometry and binding constant of fluorophores were calculated using Stern-Volmer equation and Benesi-Hildebrand plots, respectively. Structure of fluorophores were studied using DFT, B3LYP/6-311 + + G(d,p) level basis set. Quenching mechanisms and electrical properties of fluorophores were explained with theoretical outcomes. Iodine doped and undoped oligoesters electrical conductivity were studied in solid-state and the conductivity was gradually increased with increase the contact time of iodine with oligoesters. At different frequencies and temperatures, the dielectric measurement was calculated using the two-probe method. Among all oligoesters, DMDAP exhibited high electrical conductivity and DMDMP has a higher dielectric constant value than other oligoesters.

A coumarin hydrazone appended rotatable phenolic scaffold as fluorescent chemosensor for Ag+ ions and its bio imaging applications.

A coumarin hydrazone-phenol conjugate, COH4 was designed, synthesized and utilized for the cation sensing studies by fluorimetry studies. The synthesized chemosensor was completely characterized by the usual spectroscopic and analytical studies. The COH4 receptor was examined for the detection of metal ions, in which it had a noticeable blue shifted fluorescence enhancement for Ag+ ions. Upon binding towards Ag+ ions, the photoinduced electron transfer (PET) process is inhibited via intramolecular charge transfer (ICT) process assisted by the arrest of the carbon-carbon single bond rotation. The binding stoichiometry of COH4 + Ag+ complexation ratio is noted to be 1:2, which was further confirmed by jobs plot method. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.41 µM and 0.13 µM respectively. Moreover, COH4 was successfully utilized for the practical applications of Ag+ ion detection in bacterial cell lines.

Positional Isomeric Symmetric Dipodal Receptors Dangled with Rotatable Binding Scaffolds: Fluorescent Sensing of Silver Ions and Sequential Detection of l-Histidine and Their Multifarious Applications.

Three simple dipodal artificial acyclic symmetric receptors, SDO, SDM, and SDP, driven by positional isomerism based on xylelene scaffolds were designed, synthesized, and characterized by 1H NMR, 13C NMR, and mass spectroscopy techniques. Probes SDO, SDM, and SDP demonstrated selective detection of Ag+ metal ions and amino acid l-histidine in a DMSO-H2O solution (1:1 v/v, HEPES 50 mM, pH = 7.4). The detection of Ag+ metal ions occurred in three ways: (i) inhibition of the photoinduced electron-transfer (PET) process, (ii) blueshifted fluorescence enhancement via the intramolecular charge-transfer (ICT) process, and (iii) restricted rotation of the dangling benzylic scaffold following coordination with a Ag+ metal ion. Job's plot analysis and quantum yields confirm the binding of probes to Ag+ in 1:1, 1:2, and 1:2 ratios with LODs and LOQs found to be 1.3 µM and 3.19 × 10-7 M, 6.40 × 10-7 and 2.44 × 10 -6 M, and 9.76 × 10-7 and 21.01 × 10-7 M, respectively. 1H NMR titration, HRMS, ESI-TOF, IR analysis, and theoretical DFT investigations were also used to establish the binding stoichiometry. Furthermore, the probes were utilized for the detection of Ag+ ions in water samples, food samples, soil analysis, and bacterial imaging in Escherichia coli cells and a molecular logic gate was constructed.

A photoswitchable "turn-on" fluorescent chemosensor: Quinoline-naphthalene duo for nanomolar detection of aluminum and bisulfite ions and its multifarious applications.

A quinoline-naphthalene duo-based Schiff base probe (R) was synthesized and characterized by the usual spectroscopic and single-crystal X-ray crystallographic techniques. Probe R detects Al3+ and HSO3- ions via the fluorescent turn-on approach by dual pathways i.e., i) when probe R interacts with Al3+, the restriction of CN single bond rotation, blocking of both photoinduced electron transfer (PET) and CN isomerization were observed, and ii) when the sensor R interacts with HSO3-, imine (CH = N) bond was cleaved via hydrolysis and produced the respective aldehyde and amine behaving as a chemodosimeter. The binding stoichiometric ratio of R + Al3+ (1:1) was confirmed by Job's plot, emission titration profile, NMR, and mass spectrometric analyses. This probe R is highly selective to both Al3+ -ions and HSO3- -ions, without any interference of other potentially competing cations and anions. Limit of detection (LOD) and quantification (LOQ) of R with Al3+ and HSO3- were downed to nanomolar concentrations, which is much lower than the recommended level of drinking water/food fixed by the World Health Organization (WHO). Furthermore, probe R was utilized in the detection of Al3+ and HSO3- ions in highly contaminated real samples, bioimaging in E. coli cells, multiple-targeting molecular logic gate, and in bovine serum albumin (BSA) binding.

Graphene oxide-rhodamine nanocomposite for picomolar detection of chromium(III) by fluorimetry and its biofilm inhibition.

Graphene oxide-rhodamine B hydrazide (GO-RhB) nanocomposite was prepared by a simple chemical method and characterized by various spectroscopic and analytical techniques. GO-RhB nanocomposite potentially detects Cr3+ ion (excitation/emission = 550 nm/572 nm) via fluorescence turn "on-off" approach. This composite showed high binding affinity (106 M-1) with Cr3+ and a+ limit of detection (LOD) down to picomolar concentration (LOD = 85.6 pM). As far as we know, this is the first report for the sensing of Cr3+ ion at picomolar concentration. GO-RhB selectively senses Cr3+ ion without any interference of other coexisting metal ions. In addition, this composite exhibited the dynamic nature of quenching in the presence of Cr3+ ion, which is confirmed by the Stern-Volmer plot, fluorescence temperature profiles, and decay time experiments. The GO-RhB nanocomposite-based fluorescent probe was successfully applied to the quantitative detection of Cr3+ ion in milk sample (linear range = 2 to 10 nM) with better performance than other existing methods. Besides, this GO-RhB composite showed better antibiofilm activity against Acinetobacter baumannii and methicillin-resistant Staphylococcus aureus (MRSA) by using the Congo red agar and tube method.

Rhodanine-based fluorometric sequential monitoring of silver (I) and iodide ions: Experiment, DFT calculation and multifarious applications.

A simple rhodanine derived fluorophoric unit has been designed for selective detection of Ag+ and I- ions in DMSO-H2O medium. The sensor R1 showed an obvious "turn-on" fluorescence response toward Ag+ due to the inhibition of both C-N single bond free rotation, internal charge transfer (ICT) and the formation of chelation enhanced fluorescence (CHEF) effects. The fluorescence quantum yield (Φ) was increased from 0.0013 to 0.032 for receptor R1 upon the Ag+-complexation. In addition, the 1:1 complexing stoichiometry was employed based on Job's plot analysis with detection limit of 24.23 × 10-7 M. Conversely, receptor R1+Ag+ particularly detects I- ion over other co-existing anions by the "turn-off" fluorescence response due to the formation of AgI, displacing the receptor R1 with the quantum yield of 0.0014. The detection limit was calculated to be 22.83 × 10-7 M. The sensing behaviour of receptor R1 toward Ag+ was also supported by density functional theory (DFT) calculations. Moreover, the sensing ability of reported receptor R1 could be exercised in multifarious applications like paper strip, silica-supported analysis, staining test for latent finger print, logical behaviour, smartphone-assisted quantitative detection and real water samples studies.

Adsorption of nickel ions from electroplating effluent by graphene oxide and reduced graphene oxide.

Heavy metal pollution in the water bodies causes a serious threat to all living beings. Extended exposure of heavy metals such as nickel (Ni) ions causes cancer. Henceforth, the current study investigated the removal of Ni ions from the electroplating effluent using nanocomposites namely, Graphene Oxide (GO) and Reduced Graphene Oxide (rGO) in the presence of various factors such as contact time, pH, agitation speed and sorbent dosage. Further, it was determined the rate kinetic model and adsorption equilibrium isotherms. The study also focused on comparing the removal efficiency of two nanocomposites. The maximum sorption efficiency were found to be 90.8% and 84.4% at optimized pH (8), contact time (180-1440 m), RPM (250-300) and adsorbent dosage (0.2 mg/L) for GO and rGO respectively. Furthermore, toxicity of treated and untreated effluent were tested against Phosphobacter and Azospirillium using GO and rGO and found that the treated effluent was non-toxic. The contribution of this study to agriculture in using recycled effluent for crop cultivation was being verified by seed germination of Lablab purpureus seeds watered with treated and untreated effluent. Finally we concluded that the results of treated water can be used for cultivation as there was healthy growth of plants.

Novel Quinoline-Based Thiazole Derivatives for Selective Detection of Fe3+, Fe2+, and Cu2+ Ions.

New quinoline-based thiazole derivatives QPT and QBT were synthesized and characterized by various spectroscopic and single-crystal X-ray crystallographic studies. The metal-sensing properties of the probes were further examined by absorption and fluorescence spectrometry. The fluorescence intensity of QPT and QBT was remarkably quenched during the addition of Fe3+, Fe2+, and Cu2+ ions in THF/H2O (1:1) at pH = 7.4 in HEPES buffer, while the addition of other metal ions did not affect the fluorescence intensity of the ligands. The detection ability of the probes QPT and QBT was further investigated by titration with various equivalents of metal ions, optimized pH ranges for detection, and reversibility with Na2EDTA for biological applications.

Experimental and Theoretical Studies on a Simple S-S-Bridged Dimeric Schiff Base: Selective Chromo-Fluorogenic Chemosensor for Nanomolar Detection of Fe2+ & Al3+ Ions and Its Varied Applications.

A simple S-S (disulfide)-bridged dimeric Schiff base probe, L, has been designed, synthesized, and successfully characterized for the specific recognition of Al3+ and Fe2+ ions as fluorometric and colorimetric "turn-on" responses in a dimethylformamide (DMF)-H2O solvent mixture, respectively. The probe L and each metal ion bind through a 1:1 complex stoichiometry, and the plausible sensing mechanism is proposed based on the inhibition of the photoinduced electron transfer process (PET). The reversible chemosensor L showed high sensitivity toward Al3+ and Fe2+ ions, which was analyzed by fluorescence and UV-vis spectroscopy techniques up to nanomolar detection limits, 38.26 × 10-9 and 17.54 × 10-9 M, respectively. These experimental details were advocated by density functional theory (DFT) calculations. The practical utility of the chemosensor L was further demonstrated in electrochemical sensing, in vitro antimicrobial activity, molecular logic gate function, and quantification of the trace amount of Al3+ and Fe2+ ions in real water samples.

An efficient new dual fluorescent pyrene based chemosensor for the detection of bismuth (III) and aluminium (III) ions and its applications in bio-imaging.

A new simple pyrene based schiff base chemosensor 1 (nicotinic acid pyren-1-ylmethylene-hydrazide) has been constructed and is prepared from 1-pyrenecarboxaldehyde and nicotinic hydrazide. Notably, the chemosensor 1 exhibited remarkable colour changes while in the presence of trivalent metal ions like Bi3+ & Al3+ ion in DMSO-H2O, (1:1 v/v, HEPES = 50 mM, pH = 7.4). The UV-Vis spectral investigation of chemosensor 1 showed that the maximum absorption peak appeared at 378 nm. In emission studies, chemosensor 1 develops weak fluorescence, while upon the addition of Bi3+ and Al3+ ions, it exhibits an enhancement of fluorescence intensity. Nevertheless, rest of metal ions have no changes in the emission spectra. The association constant of chemosensor 1 for binding to Bi3+ & Al3+ system had a value of 1.27 × 104 M-1 and 1.53 × 104 M-1. The detection limits were 0.12 µM for Bi3+ and 0.17 µM for Al3+ respectively. The overall results reveal that chemosensor 1 can act as a dual-channel, highly selective, and sensitive probe for Bi3+ and Al3+ ions. Moreover, the fluorescence imaging of chemosensor 1 was applied in RAW 264.7 cell line and cytotoxicity assay prove that this chemosensor 1 is non-toxic as well as highly biocompatible.

Sol-Gel Synthesis of Ce4-x Sr1+x Fe5-x Zn x O14+δ [0 ≤ x ≤ 0.45] Superparamagnetic Oxide Systems and Its Magnetic, Dielectric, and Drug Delivery Properties.

In this work, we have successfully synthesized superparamagnetic nanocomposites, Ce4-x Sr1+x Fe5-x Zn x O14+δ (0 ≤ x ≤ 0.45) (CSFZ) (TA1-TA4: x = 0, 0.15, 0.30, and 0.45) via the Nitrate-citrate sol-gel method. X-ray diffraction studies show the formation of single-phase nanocomposites (NCs) and the average crystallite size is found to be 18 nm. Energy-dispersive X-ray spectroscopy analysis supports the formation of the desired product with the expected composition. The scanning electron microscopy image shows that the prepared samples are in spherical shape and highly porous in nature. Most of the particle sizes present in the image are in the range of 5-20 nm. The optical studies show an intense peak at 583 nm corresponding to the instantaneous existence of both Fe2+ and Fe3+ intervalence electronic charge transition bands. X-ray photoelectron spectra analysis confirms the presence of elements with their preferred oxidation state. The superparamagnetic nature of the prepared sample was confirmed by vibrating sample magnetometer analysis. Synthesized materials show a low saturate magnetic moment ranging from 0.3400 to 0.1075 emu/g. The coercivity and retentivity value of the synthesized NC is zero. The NCs show high encapsulation efficiency toward ciprofloxacin hydrochloride because of their unique structure and release the loaded drug molecules in a sustained manner up to 10 h at pH 7.4. Such NCs have high potential for use as multifunctional material in various fields such as optical properties, conductivity studies, dielectric, sensor, and drug delivery properties.

New palladium(II) hydrazone complexes: Synthesis, structure and biological evaluation.

Two new palladium(II) complexes of 4-hydoxy-benzoic acid (5-bromo-2-hydroxy-benzylidene)-hydrazide (H2L) (1) with triphenylphosphine and triphenylarsine as coligand have been synthesized and characterized by the aid of various spectral techniques. The structure of the ligand and complexes was confirmed by single crystal X-ray diffraction studies. The hydrazone ligand acts as a tridendate ligand with ONO as the donor sites and is preferably found in the enol form in all the complexes. The structural analysis of 2 and 3 confirms the square planar geometry of the two complexes. The DNA binding of these complexes and ligand calf thymus DNA (CT-DNA) was investigated by using various methods, which revealed that the compounds interacted with CT-DNA through intercalation. Binding properties of the free ligand and its complexes with bovine serum albumin (BSA) protein have been investigated using UV-visible and fluorescence spectroscopic methods which indicated the stronger binding nature of the palladium complexes to BSA than the free hydrazone ligand. In addition, concentration dependent free radical scavenging potential of all the synthesized compounds (1-3) was also carried out under in vitro conditions. Further, the in vitro cytotoxicity of the compounds was examined on a HeLa and MCF-7 cell lines, which revealed that complex 2 exhibited a superior cytotoxicity than complex 3 and ligand 1.

Synthesis, structure, DNA/BSA interaction and in vitro cytotoxic activity of nickel(II) complexes derived from S-allyldithiocarbazate.

Two nickel(II) complexes with formula NiL1 and NiL2 (HL1 = S-allyl-4-methoxybenzylidene hydrazinecarbodithioate, HL2 = S-allyl-1-napthylidenehydrazinecarbodithioate) have been synthesized and characterized by elemental analysis, FT-IR, NMR, UV-vis spectroscopy and ESI mass spectrometry. The crystal structure of complex 1 has been determined by single crystal X-ray diffractometry. Both HL1 and HL2 ligands are coordinated to the metal in thiolate form. In complexes, squareplanar geometry of the nickel is coordinated with two bidentate ligand units acting through azomethine nitrogen and thiolato sulfur atoms. To explore the potential medicinal value of the complexes with calf thymus DNA and bovine serum albumin (BSA) were studied at normal physiological conditions using fluorescence spectral techniques. The DNA binding constant values of the complexes were found in the range from 5.02 × 10(4), 3.54 × 10(4), and the binding affinities are in the following order 1 > 2. In addition, nickel complexes 1 and 2 shows better binding propensity to the bovine serum albumin (BSA) protein, giving a Ksv value 5.8 × 10(4), 4.47 × 10(4) respectively. From the oxidative cleavage of the complexes with pBR322 DNA, it is inferred that the effects of cleavage are dose-dependent. In addition, in vitro cytotoxicity of the complexes assayed against Vero and HeLa cell lines have shown higher cytotoxic activity with the lower IC50 values indicating their efficiency in killing cancer cells even at various concentrations.

Ruthenium(III) S-methylisothiosemicarbazone Schiff base complexes bearing PPh3/AsPh3 coligand: synthesis, structure and biological investigations, including antioxidant, DNA and protein interaction, and in vitro anticancer activities.

New Ru(III) isothiosemicarbazone complexes [RuCl(EPh3)L(1-4)] (E=P or As) were obtained from the reactions between [RuCl3(EPh3)3] and bis(salicylaldehyde)-S-methylisothiosemicarbazone (H2L(1-3))/bis(2-hydroxy-naphthaldehyde)-S-methylisothiosemicarbazone (H2L(4)) ligands. The new complexes were characterized by using elemental analyses and various spectral (UV-Vis, IR, (1)H NMR, FAB-Mass and EPR) methods. The redox properties of the complexes were studied by using cyclic voltammetric method. The new complexes were subjected to various biological investigations such as antioxidant assays involving DPPH radical, hydroxyl radical, nitric oxide radical and hydrogen peroxide, DNA/protein interaction studies and in vitro cytotoxic studies against human breast cancer cell line (MCF-7). New complexes showed excellent free radicals scavenging ability and could bind with DNA via intercalation. Protein binding studies using fluorescence spectroscopy showed that the new complexes could bind strongly with bovine serum albumin (BSA). Photo cleavage experiments using DNA of E-coli bacterium exhibited the DNA cleavage ability of the complexes. Further, the in vitro anticancer activity studies on the new complexes against MCF-7 cell line exhibited the ability of Ru(III) isothiosemicarbazone complexes to suppress the development of malignant neoplastic disease cells.

Highly enantioselective extraction of underivatized amino acids by the uryl-pendant hydroxyphenyl-binol ketone.

The hydroxyphenyl chiral ketone, (S)-3, reacts with D-amino acids bearing hydrophobic side chains exclusively over the L-amino acids in a two-phase liquid-liquid extraction, and thus acts as a highly stereoselective extractant. Calculations for the energy-minimized structures for the imine diastereomers and the comparison of the selectivities with other phenyl ketones, (S)-4 and (S)-5, demonstrate that the hydrogen bond between the carboxylate group and the phenolic hydroxyl group contributes to the remarkable enantioselectivities. The multiple hydrogen bonds present in the imine of (S)-3 reinforce the rigidity, and results in the difference between the stabilities of the imine diastereomers. The imine could be hydrolyzed in methanolic HCl solution, and the extraction of the evaporated residues revived the organic layer of (S)-3, which could enter into a new extractive cycle and leaves the D-amino acid with enantiomeric excess (ee) values of over 97 % in the aqueous layer.

Synthesis, characterization and crystal structure of cobalt(III) complexes containing 2-acetylpyridine thiosemicarbazones: DNA/protein interaction, radical scavenging and cytotoxic activities.

The synthesis, structure and biological studies of cobalt(III) complexes supported by NNS-tridentate ligands are reported. Reactions of 2-acetylpyridine N-substituted thiosemicarbazone (HL(1-3)) with [CoCl2(PPh3)2] resulted [Co(L(1-3))2]Cl (1-3) which were characterized by elemental analysis and various spectral studies. The molecular structure of the complex 1 has been determined by single crystal X-ray diffraction studies. In vitro DNA binding studies of complexes 1-3 carried out by fluorescence studies and the results revealed the binding of complexes to DNA via intercalation. The binding constant (Kb) values of complexes 1-3 from fluorescence experiments showed that the complex 3 has greater binding propensity for DNA. The DNA cleavage activity of the complexes 1 and 3 were ascertained by gel electrophoresis assay which revealed that the complexes are good DNA cleavage agents. Further, the interactions of the complexes with bovine serum albumin (BSA) were also investigated using fluorescence spectroscopic method, which showed that the complexes 1-3 could bind strongly with BSA. The antioxidant property of the complexes was evaluated to test their free-radical scavenging ability. Furthermore, in vitro cytotoxicity of the complexes against MCF-7 and A431 cell lines was assayed which showed higher activity and efficiently vanished the cancer cells even at low concentrations.

BINO(L)-based chiral receptors as fluorescent and colorimetric chemosensors for amino acids.

Three representative BINOL derivatives were examined for their chiral recognitions with D- and L-t-Boc-amino acid anions: an open system 1, which bears two urea groups and two pyrene groups; a closed ring system 2, which bears two urea groups with a closed ring system; and a dimeric system 3, which bears two benzylic amine groups and two pyrene groups. Dimeric system 3 displayed a ΔI(D)/ΔI(L) of 12.95 for t-Boc-alanine.

Zn(2+)-induced conformational changes in a binaphthyl-pyrene derivative monitored by using fluorescence and CD spectroscopy.

We have developed a unique binaphthyl-pyrene system 1, whose dihedral angle is reversibly modulated by the addition of Zn(2+). Dihedral angle changes in this system were monitored by using circular dichroism (CD) and by an observed "off-on" fluorescence enhancement in aqueous solution. Owing to these changes, the presence of biologically important Zn(2+) ions in samples can be readily monitored by employing CD and fluorescence spectroscopy. Finally, the experimental observations made in this effort are supported by the results of quantum mechanical calculations.

Enantioselective liquid-liquid extractions of underivatized general amino acids with a chiral ketone extractant.

The chiral ketone (S)-3 shows high kinetic enantioselectivities toward the L form for general underivatized amino acids with hydrophobic side chains and a high thermodynamic enantioselectivity toward the D form for cysteine with its -SH polar side chain when used as an extractant in enantioselective liquid-liquid extractions in the presence of Aliquat 336. Consecutive extractions by imine formation and hydrolysis increase the enantiopurity of the amino acid, as both of these reactions are L-form-selective.