Tri-armed Schiff base fluorescent sensor for the rapid recognition of Zn(II): application in live cell imaging, test strips and TLC.

Various metal ions exist in nature and human beings and play limitless vital roles in both the atmosphere and biology. A fundamental and useful aspect is the qualitative and quantitative assessment of Zn(II) at concentration levels as low as parts per billion (ppb). Thus, the design and development of novel fluorescent turn-on receptors have gained significant interest because of their potential for use in live cell imaging to detect biologically relevant metal ions with high selectivity and sensitivity. The present research illustrates the design and synthesis of a novel fluorescent sensor [(1,3,5-triazine-2,4,6-triyl)tris(hydrazine-2-yl-1-ylidene)tris(methaneylylidene)]tris(2,4-di-tert-butylphenol) (THDBP) for the selective and sensitive probing of Zn(II). The sensor exhibited a fluorescence turn-on mechanism upon treatment with Zn(II) ions at λemi. 503 nm in aq. acetonitrile. The formation of a 1 : 3 complex between THDBP and Zn(II) is confirmed from the Job plot and ESI-MS spectrum. The evaluated limit of detection (LOD) and association constant (Ka) of the sensor THDBP for Zn(II) were found to be 1.03 × 10-10 M and 2.33 × 108 M-1, respectively. Further research demonstrates the practical application of the sensor for the detection of Zn(II) ions in live cells. The sensing ability of the sensor THDBP was also explored through inexpensive test strips and TLC sheets.

A pyrene-induced PET-based chemosensor for biologically important Zn(II) ions: application in test strips and live cell imaging studies.

Cation and anion sensing is vital owing to their universal dispersion in ecosystems and biological functions. It has been shown that fluorescent receptors based on organic platforms are efficient for detecting a number of ions and have many advantages such as low cost, superior sensitivity and simplicity in installation. This study demonstrates the design and synthesis of a novel receptor (E)-3-[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]-2-(pyren-1-yl)-2,3-dihydroquinazolin-4(1H)-one (DTQ) for the rapid recognition of Zn(II) ions. DTQ exhibited a significant fluorometric "turn-on" characteristic towards Zn(II) at λmax 444 nm in aqueous acetonitrile by inhibiting the photo-induced electron transfer (PET) and -CN- process. The ESI-MS analysis and Job's plot experimental results confirmed stoichiometric 1 : 1 complex formation between DTQ and Zn(II). Fluorometric investigations revealed the detection limit and association constant of DTQ towards Zn(II), which were found to be 13.4 nM and 1.47 × 105 M-1, respectively. DTQ was employed to sense Zn(II) on low-cost test strips. The present research findings imply that DTQ can function as an effective sensor for Zn(II).

Luminescent Pyrene-based Schiff base Receptor for Hazardous Mercury(II) Detection Demonstrated by Cell Imaging and Test Strip.

Qualitative and quantitative analysis of mercury at concentration levels as low as parts per billion (ppb) is a basic and practical concern. The vast majority of research in this field has centered on the development of potent chemosensor to monitor mercuric (Hg2+) ions. Mercury exists in three oxidation states, + 2, + 1 and 0, all of which are highly poisonous. In this study, (N1E,N2E)-N1,N2-bis(pyrene-1-ylmethylene)benzene-1,2-diamine (PAPM), a novel photoluminescent sensor based on pyrene platform was synthesized. Over the tested metal ions (Cd2+, Co2+, Cu2+, Mg2+, Mn2+, Ni2+, K+, Na+, Zn2+, Sr2+, Pb2+, Al3+, Cr3+ and Fe3+) the sensor responds only to Hg2+ by showing high selectivity and sensitivity. After treatment with mercuric ions at room temperature, the luminescence intensity of probe was quenched at 456 nm. The quenching of fluorescence intensity of probe upon addition of mercury is due to the effect of "turn-off" chelation enhanced quenching (CHEQ) by the formation of 1:1 complex. The ESI-MS spectrum and the Job's experimental results confirm the formation of 1:1 complex between PAPM and Hg2+. The detection limit and association constant of sensor for mercury is computed using fluorescence titration data and were found to be 9.0 × 10-8 M and 1.29 × 105 M-1 respectively. The practical application of sensor towards recognition of mercury(II) ions was explored through economically viable test strips and also using cell imaging studies.

Effect of Hydroxyl Group on Photo-Physical Properties and Dipole Moments of Fluorescent Dyes: An Experimental and Computational Approach.

In this work, structurally similar, (E)-N'-(2-hydroxybenzylidene)-3,5-di-tert-butyl-2-hydroxybenzohydrazide (A) and (E)-N'-(2-4-dihydroxybenzylidene)-3,5-di-tert-butyl-2-hydroxybenzohydrazide (A-OH) dyes dissolved in general solvents have been studied to explore photo-physical properties, employing solvatochromic shift method, thereby determining their dipole moments in the ground (µg) and excited (µe) states. The molecule A shows a bathochromic shift of fluorescence emission maxima in aprotic solvents whereas a hypsochromic shift in protic solvents. Interestingly, A-OH follows a hypsochromic shift in both protic and aprotic solvents with increasing solvent polarity. The effect of hydroxyl substituent on UV-Visible absorption, fluorescence emission, and dipole moment of the titled organic molecules was explained. Theoretical methods such as Bilot-Kawski method for determination of µg and µe and Bakshiev, Kawski-Chamma-Viallet, Lippert-Mataga equations for µe, and Reichardt method for the difference between µg and µe were employed. It is observed that µe is higher than that of µg for both the molecules, and interestingly, upon substituting an additional hydroxyl group the value of µg has increased while µe is decreased. The DFT calculations have been performed to support experimental results by employing DFT/B3LYP/6-311G + (d) and TD-DFT/B3LYP/6-311G + (d) method using Gaussian09 software. The electrophilic and nucleophilic sites on the molecules were studied with the help of MEP. The NBO analysis results show that the interaction N24 (σ) → C22-O23 (π*) is found to be stronger in both the molecules with energy 68.90 kJ/mol and the effect of hydroxyl group is also discussed on the basis of HOMO and LUMO.

Mixed ligand complex via zinc(II)-mediated in situ oxidative heterocyclization of hydrochloride salt of 2-chlorobenzaldehyde hydralazine hydrazone as potential of antihypertensive agent.

An unusual tetrahedral mixed ligand Zn(II) complex ZnT(L)Cl, where L = 2-chlorobenzaldehyde hydralazine hydrazone and T = in situ generated 3-(2-chlorophenyl)-1,2,4-triazolo[3,4-a]phthalazine is reported. Structure of the fused triazole has been confirmed by single crystal X-ray diffraction studies. Structure of Co(II), Ni(II), Cu(II) and Zn(II) complexes has been confirmed by spectral and analytical methods. Metal complexes have exhibited better activity in the fructose induced hypertension studies in animal model and are comparable with the standard.

Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes.

The coordinating behavior of a new dihydrazone ligand, 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with α=98.491(10)°, ß=110.820(10)° and γ=92.228(10)°. The cell dimensions are a=10.196(7)Å, b=10.814(7)Å, c=10.017(7)Å, Z=2 and V=1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with g(iso)=2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible.

Spectroscopic, magnetic and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes of 3-acetylcoumarin-isonicotinoylhydrazone and their antimicrobial and anti-tubercular activity evaluation.

Co(II), Ni(II), Cu(II) and Zn(II) complexes with a new heterocyclic Schiff base derived by the condensation of isonicotinoylhydrazide and 3-acetylcoumarin have been synthesized. ¹H, ¹³C and 2D HETCOR NMR analyses confirm the formation of title compound and existence of the same in two isomeric forms. The metal complexes were characterized on the basis of various spectroscopic techniques like electronic, EPR, IR, ¹H and ¹³C NMR studies, elemental analysis, magnetic properties and thermogravimetric analysis, and also by the aid of molar conductivity measurements. It is found that the Schiff base behaves as a monobasic tridentate ligand coordinating in the imidol form with 1:1 metal to ligand stoichiometry. Trigonal bipyramidal geometry has been assigned for Ni(II) and Cu(II) complexes, while tetrahedral for Co(II) and Zn(II) complexes. The compounds were subjected to antimicrobial and anti-tubercular activity screening using serial broth dilution method and Minimum Inhibitory Concentration (MIC) is determined. Zn(II) complex has shown significant antifungal activity with an MIC of 6.25 µg/mL while Cu(II) complex is noticeable for antibacterial activity at the same concentration. Anti-TB activity of the ligand has enhanced on complexation with Co(II) and Ni(II) ions.

Transition metal complexes of 3-aryl-2-substituted 1,2-dihydroquinazolin-4(3H)-one derivatives: new class of analgesic and anti-inflammatory agents.

Five-coordinate, neutral transition metal complexes of newly designed pyridine-2-ethyl-(3-carboxylideneamino)-3-(2-phenyl)-1,2-dihydroquinazolin-4(3H)-one (L) were synthesized and characterized. The structure of ligand is confirmed by single crystal X-ray diffraction studies. The compounds were evaluated for the anti-inflammatory activity by carrageenan-induced rat paw edema model while their analgesic activity was determined by acetic acid-induced writhing test in mice wherein the transition metal complexes were found to be more active than the free ligand.

Synthesis, characterization of copper(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) complexes of [7-hydroxy-4-methyl-8-coumarinyl]glycine and a comparitive study of their microbial activities.

A new Mannich base, [7-hydroxy-4-methyl-8-coumarinyl]glycine [MCGH(2)], has been prepared by the condensation of 7-hydroxy-4-methyl-coumarin with glycine and formaldehyde. Its conformational changes on complexation with transition metal ions [copper(II), cobalt(II), nickel(II), zinc(II) and cadmium(II)] have been studied on the basis of elemental analysis, conductivity measurements, spectral (infrared, (1)H NMR, electronic, EPR), magnetic and thermogravimetric studies. The infrared spectral studies of all the complexes reveal that the ligand has coordinated through -NH and two hydroxyl groups. The conductance data of the complexes suggest them to be non-electrolytes. Fluorescence property of the ligand and its metal complexes was studied and concluded that the ligand MCGH(2) can be a potential candidate for the determination of zinc(II) and cadmium(II) at room temperature by fluorimetric method. The antimicrobial activity of all the compounds was studied against Gram negative (Escherichia coli) and Gram positive (Bacillus cirroflagellosus) bacteria and fungi, Aspergillus niger and Candida albicans. It was observed that the coordination of metal ion has a pronounced effect on the microbial activities of the ligand. All the metal complexes have shown higher antimicrobial effect than the free ligand.

Antimicrobial Study of Newly Synthesized Lanthanide(III) Complexes of 2-[2-hydroxy-3-methoxyphenyl]-3-[2-hydroxy-3-methoxybenzylamino]-1,2-dihydroquinazolin-4(3H)-one.

New lanthanide(III) complexes with 2-[2-hydroxy-3-methoxyphenyl]-3-[hydroxyl-3-methoxybenzylamino]-1,2-dihydroquin- azoline-4(3H)-one (Hmpbaq) have been synthesized and characterized by elemental analysis, conductance measurements, magnetic susceptibilities, spectroscopic (IR, NMR, UV, EPR), and thermal studies. Molar conductance studies indicate 1 : 1 electrolytic behavior for these complexes. IR spectra indicate that Hmpbaq acts as a tridentate ligand coordinating through carbonyl oxygen, benzyl amine nitrogen, and deprotonated phenolic oxygen. TG and DTA studies of La(III) and Pr(III) complexes indicate the presence of two coordinated water molecules. Based on these studies, the complexes have been formulated as [La(mpbaq)(2)(H(2)O)(2)].NO(3), where Ln = La(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Th(III), Dy(III), and Y(III). The ligand, lanthanide(III) salts, and the corresponding complexes have been simultaneously screened for their antibacterial and antifungal activities and compared with the drugs in use.

X-ray crystal structure of phenylglycine hydrazide: synthesis and spectroscopic studies of its transition metal complexes.

Phenylglycine hydrazide was synthesized and investigated by X-ray crystallography. It crystallizes in the monoclinic space group P121/c with cell parameters a=5.9459 (18) Angstrom, b=5.1940 (16) Angstrom, c=26.7793 (83) Angstrom and Z=2. Its conformational changes, on complexation with transition metal ions Cu(II), Co(II), Ni(II), Mn(II) and Zn(II) has been studied on the basis of elemental analysis, magnetic moment and spectral (IR, (1)H NMR, UV-vis) studies. The bidentate nature of the ligand was confirmed on the basis of a comparative IR and NMR spectral studies. The trigonal bipyramidal geometries were observed for Cu(II), Ni(II) and Co(II) complexes, while it is octahedral for the remaining complexes. The conductivity data suggest them to be non-electrolytes.

Trinuclear lanthanide complexes of a compartmental ligand N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide: a spectroscopic investigation.

Trinuclear lanthanide complexes of the formula [Ln(3)(PPDA)(NO(3))(6)(H(2)O)(2)].NO(3).2H(2)O where Ln=La(III), Pr(III), Sm(III), Nd(III), Eu(III) Gd(III) Tb(III), Dy(III) and Y(III); H(2)PPDA=N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide, have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility measurements and spectral (IR, NMR, UV-vis, fluorescence, FAB and EPR) and thermal studies.

Lanthanide(III) and Yttrium(III) Complexes of Benzimidazole-2-Acetic Acid: Synthesis, Characterisation and Effect of La(III) Complex on Germination of Wheat.

The synthesis and characterisation of lanthanide(III) and yttrium(III) nitrate complexes of benzimidazole-2-acetic acid (HBIA) are reported. The complexes have been characterised by elemental analysis, molar conductance, magnetic studies, IR, (1)H NMR, UV-visible, EPR, and TG/DTA studies. They have the stoichiometry [Ln(3)(BIA)(2)(NO(3))(7)(H(2)O)(4)] . 3H(2)O where Ln=La(III), Pr(III), Nd(II), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), and Y(III). The effect of La(III) complex on germination, coleoptile, and root length of two local varieties of wheat DWR-195 and GW-349 for different treatment periods has been investigated. The complex was found to exhibit enhanced activity, compared to HBIA or metal salt alone at lower treatment periods.

Synthesis, characterisation and biological evaluation of lanthanide(III) complexes with 3-acetylcoumarin-o-aminobenzoylhydrazone (ACAB).

Lanthanide(III) complexes of the general formula [Ln(ACAB)(2)(NO(3))(2)(H(2)O)(2)].NO(3).H(2)O where Ln=La(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III) and Y(III), ACAB=3-acetylcoumarin-o-aminobenzoylhydrazone have been isolated and characterised based on elemental analyses, molar conductance, IR, (1)H- and (13)C-NMR, UV, TG/DTA and EPR spectral studies. The ligand behaves in bidentate fashion coordinating through hydrazide >C=O and nitrogen of >C=N. A coordination number of ten is assigned to the complexes. Antibacterial and Antifungal studies indicate an enhancement of activity of the ligand on complexation.