Selective recognition of Fe2+ in aqueous solution by chalcones.

Recognition of metal ions in aqueous media has direct impact for designing new supramolecular hosts for targeting biochemical pathways. In the present work we have studied the binding behavior of three simple chalcones with variation in number of phenolic OH groups. These chalcones showed very good binding capabilities towards metal ions in CH3OH-H2O (1:1, v/v) solvent system. The receptors R1 has interacted with all metal ions, which are used in the present study through 2:1 mode of complexation whereas R2 have showed equilibrium between the complexes of 2:1 and 1:1 with few exceptions. The highest association constants (K21) of R1 and R2 for Fe2+ is observed as 1.1 × 109 (4) M-1 and 2.3 × 108 (7) M-1 respectively by fluorescence titration method. But R3, which is lack of any phenolic OH group, binds all the metal ions through the formation of 1:1 mode of complex formation by exploiting the only one donor site as carbonyl 'O' atom resulting lower association constant for all the metal ions. So intermolecular hydrogen bonding as well as π- π stacking interaction forced the receptors R1 and R2 to arrange in a pseudo cleft orientation for the recognition of metal ions in 2:1 mode of complex formation. The binding behaviour of the receptors with few alkali metal ions (Na+, K+ and Cs+) and alkaline-earth metal ions (Mg2+, Ca2+ and Ba2+) are also studied and observed weak binding nature in compared with the transition metal ions.

Pyrrolidine-Derived Phenanthroline Diamides: An Influence of Fluorine Atoms on the Coordination of Lu(III) and Some Other f-Elements and Their Solvent Extraction.

Three pyrrolidine-derived phenanthroline diamides were studied as ligands for lutetium trinitrate. The structural features of the complexes have been studied using various spectral methods and X-ray. The presence of halogen atoms in the structure of phenanthroline ligands has a significant impact on both the coordination number of lutetium and the number of solvate water molecules in the internal coordination sphere. The stability constants of complexes with La(NO3)3, Nd(NO3)3, Eu(NO3)3, and Lu(NO3)3 were measured to demonstrate higher efficiency of fluorinated ligands. NMR titration was performed for this ligand, and it was found that complexation with lutetium leads to an approximately 13 ppm shift of the corresponding signal in the 19F NMR spectrum. The possibility of formation of a polymeric oxo-complex of this ligand with lutetium nitrate was demonstrated. Experiments on the liquid-liquid extraction of Am(III) and Ln(III) nitrates were carried out to demonstrate advantageous features of chlorinated and fluorinated pyrrolidine diamides.

Complexation of sulfamethazine with Cd(II) and Pb(II): implication for co-adsorption of SMT and Cd(II) on goethite.

This study quantified the complex stability constants of sulfamethazine (SMT) with cadmium (Cd2+) and lead (Pb2+) under different pH conditions. The UV-Vis spectrophotometer was used for acquiring the complexation data. Results showed that the complex stability constants of SMT with cadmium (Cd2+) and lead (Pb2+) increased as a function of the solution pH. In the investigated pH range, Cd2+ showed stronger complex affinity with SMT than Pb2+. It appeared that cation-π interactions might dominate the complex between SMT with Pb2+ and Cd2+ at acid environment, and the covalent bonding might play a major role at neutral environment. Batch adsorption equilibrium experiment showed that the sorption capacity of Cd2+ on goethite increased from 3.83 to 7.64 mg/g along with the addition of 1 mg/L SMT, indicating SMT can impede the transportation of Cd. In general, this study worked out the complexation constants and clarified the complexation mechanism between SMT with lead and cadmium, while sorption experiment indicated that sorption of Cd onto goethite was enhanced with SMT.

A new colorimetric chemosensors for Cu2+ and Cd2+ ions detection: Application in environmental water samples and analytical method validation.

A new heterocyclic thiophene-2-caboxylic acid hydrazide based chemosensor R1 to R4 were designed, synthesized and characterized by various spectroscopic techniques like FT-IR, UV-Vis, 1H NMR, 13C NMR, Mass and SC-XRD. The chemosensor R3 showed a significant color change from colorless to yellow in the presence of Cu2+ ions and chemosensor R4 showed a significant color change from colorless to yellow in the presence of Cd2+ ions over the other tested cations such as Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Zn2+, Ag2+, Al3+, Pb2+, Hg2+, K+, Ca2+ and Mg2+. The high selective and sensitivity of R3 towards Cu2+ and R4 towards Cd2+ ions was confirmed by UV-Vis spectroscopic study. The R3 showed a red shift in the presence of Cu2+ ions by Δλmax 67 nm and R4 showed a red shift in the presence of Cd2+ ions by Δλmax 105 nm in the absorption spectrum. The binding stoichiometric ratio of the complex between R3 - Cu2+ and R4 - Cd2+ ions have been found to be 1:1 using the B-H plot. Under optimized experimental conditions, the R3 and R4 exhibits a dynamic linear absorption response range, from 0 to 50 µM for Cu2+ ions and 0 to 30 µM for Cd2+ ions, with the detection limit of 2.8 × 10-6 M for Cu2+ and 2.0 × 10-7 M for Cd2+ ions. The proposed analytical method for the quantitative determination of Cu2+ and Cd2+ ions was validated and successfully applied for the environmental samples with good precision and accuracy.

Multi-signaling thiocarbohydrazide based colorimetric sensors for the selective recognition of heavy metal ions in an aqueous medium.

A series of colorimetric chemosensors R1-R6 have been developed from thiocarbohydrazide derivatives, for the selective detection of heavy metal ions. The structures of the receptors R1-R6 were well characterized by standard spectroscopic techniques like FT-IR, 1H NMR, and ESI-MS. The solid structure of receptor R1 and R2 were derived by single crystal X-ray diffraction (SC-XRD). The cation reorganization abilities of receptors R1-R6 were studied by UV-Vis spectroscopy. The receptors R1, R3 and R4 acts as a tremendous sensitive probe for heavy metal ions (Hg2+, Cd2+ and Pb2+) with the µM detection (R1 for Hg2+, 2.72, R3 for Cd2+, 3.22, R4 for Hg2+, Cd2+ & Pb2+, 0.70, 0.20 & 0.30µM) and the receptors R2, R5 &R6 are sensitive towards Cu2+ ions with the µM detection (3.34, 0.90 & 1.20µM) in an aqueous medium among all other tested cations. The receptor R4 shows a multi-color response towards Hg2+, Cu2+, Cd2+ and Pb2+ ions. The recognition mechanism, stoichiometric binding ratio and detection limit (DL) have been examined by UV-Visible spectroscopic titration experiments and Benesi-Hildebrand (B-H) plot, receptor R1-R6 sowed 1:1 binding ratio with good binding constant range of 103 to 105M-1 with Hg2+, Cu2+, Cd2+ and Pb2+ ions metal ions.