Effect of Pendant Group Length Upon Metal Ion Complexation in Acetonitrile by Di-Ionized Calix[4]Arenes Bearing Two Dansyl Fluorophores

A series of three di-ionizable calix[4]arenes with two pendant dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims was synthesized. Structures of the three ligands were identical except for the length of the spacers which connected the two dansyl groups to the calix[4]arene scaffold. Following conversion of the ligands into their di-ionized di(tetramethylammonium) salts, absorption and emission spectrophotometry were utilized to probe the influence of metal cation (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mn²⁺, Pb²⁺, Zn²⁺ and Fe³⁺) complexation in acetonitrile. Upon complexation with these metal cations, emission spectra underwent marked red shifts and quenching of the dansyl group fluorescence for the di-ionized ligand with the shortest spacer. A similar effect was noted for the di-ionized ligand with an intermediate spacer for all of the metal ions, except Ba²⁺. For the di-ionized ligand with the longest spacer, the metal cations showed different effects on the emission spectrum. Li⁺, Mg²⁺, Ca²⁺ and Ba²⁺ caused enhancement of emission intensity with a red shift. Other metal cations produce quenching with red shifts in the emission spectra. Transition metal cations interacted strongly with all three di-ionized ligands. In particular, Fe³⁺ and Hg²⁺ caused greater than 99% quenching of the dansyl fluorescence in the di-ionized ligands.     

Interaction studies of cysteine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cation complexes

The coordination geometries, electronic features, metal ion affinities, entropies, and the energetics of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with different possible conformations of cysteine complexes were studied. The complexes were optimized using density functional theory (B3LYP) and second order Moller–Plesset Perturbation (MP2) theory methods using 6‐311 + +G** basis set. The interactions of the metal cations at different nucleophilic sites of cysteine conformations were considered after a careful selection among several binding sites. All the metal cations coordinate with cysteine in a tridentate manner and also the most preferred position for the interaction. It is found that, the overall structural parameters of cysteine are not altered by metal ion substitution, but, the metal ion‐binding site has undergone a noticeable change. All the complexes were characterized by an electrostatic interaction between ligand and metal ions that appears slightly more pronounced for lithium and beryllium metal complexes. The metal ion affinity (MIA) and basis set superposition error (BSSE) corrected interaction energy were also computed for all the complexes. The effect of metal cations on the infrared (IR) stretching vibrational modes of amino N? H bond, side chain thiol group S? H bond, hydroxyl O? H bond, and Carbonyl C?O bond in cysteine molecules have also been studied. The nature of the metal ion‐ligand bond and the coordination properties were examined using natural bond order (NBO) at bond critical point (electron density and their Laplacian of electron density) through Atoms in Molecules (AIM) analyses. Copyright © 2010 John Wiley & Sons, Ltd.     

Interaction of cations with 2′‐deoxythymidine nucleoside and analysis of the nature and strength of cation bonds

Binding of Mg²⁺, Ca²⁺, Zn²⁺, and Cu⁺ metal ions with 2′‐deoxythymidine (dT) nucleoside was studied using a density functional theory method and a 6‐311++G(d,p) basis set. This work demonstrated that the interaction of dT with these cations is tri‐coordinated η (O2, O4′, O5′). Among the four types of cations, Zn²⁺ cation exhibited the most tendency to interact with the dT. Cations via their interaction with dT can affect the N‐glycosidic bond length, the values of pseudorotation of the sugar ring, the orientation of the base unit with respect to the sugar ring, and the acidity of the O5′H, O3′H, and N3H groups in the dT nucleoside. Natural bond orbital analysis was performed to calculate the charge transfer and natural population analysis of the complexes. Quantum theory of atoms in molecules was also applied to determine the nature of interactions. It was shown that in dT–Mg²⁺ and dT–Ca²⁺ complexes, the bonds are electrostatic (closed‐shell) interactions, although they are partially covalent and partially electrostatic interactions in dT–Zn²⁺ and dT–Cu⁺ complexes. Copyright © 2011 John Wiley & Sons, Ltd.     

A Novel Naphthalene-Immobilized Nanoporous SBA-15 as a Highly Selective Optical Sensor for Detection of Fe<Superscript>3+</Superscript> in Water

A novel organic-inorganic hybrid optical sensor (SBA-NCO) was designed and synthesized through immobilization of isocyanatopropyl-triethoxysilane and 1-amino-naphthalene onto the surface of SBA-15 by post-grafting method. The characterization of materials using XRD, TEM, N₂ adsorption-desorption, and FT-IR techniques confirmed the successful attachment of organic moieties and preserving original structure of SBA-15 after modification step. Fluorescence experiments demonstrated that SBA-NCO was a highly selective optical sensor for the detection of Fe³⁺ directly in water over a wide range of metal cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ in a wide pH values.     

Comparison of the stability of thymine tautomers and the interaction of its tautomers with Na+, K+, Mg2+ and Ca2+ in gas and solvent phases

The present study compared the interactions among Na ⁺, K ⁺, Mg²⁺ and Ca²⁺, thymine and its tautomers in the gas and solvent phase, an interaction dependent upon the electronic construction of the tautomers. Three types of cation interaction with thymine and its tautomers were observed. In the first one, the metal cations interacted with a lone pair of nitrogen or oxygen of the tautomers. In the second type, there was an interaction among the cations, nitrogen and oxygen at the same time; the last one was that of cations with the electron density of thymine π-system, where the cations were perpendicular to the ring of thymine. The interaction of metals cation with tautomers was studied in the gas and solvent phases; a comparison was then made between interactions in two phases. The interaction energy for all complexes indicated the stability of complexes, an energy which was higher in Ca²⁺ and Mg²⁺ compared with Na⁺ and K⁺. Concerning K⁺ and Na⁺, the stability of all complexes of tautomers was greater than that of thymine complexes; however, the stability of certain Ca²⁺ and Mg²⁺ complexes was lower than the complexes of thymine.     

Selective Recognition of Cobalt (II) Ion by a New Cryptand Compound with N2O2S2 Donor Atom Possessing 2-Hydroxy-1-Naphthylidene Schiff Base Moiety

A new cryptand compound carrying 2-hydroxy-1-naphthylidene Schiff base moiety (3) was designed and synthesized by reaction of the corresponding macrobicyclic amine compound (1) and 2-hydroxy-1-naphthaldehyde (2). The influence of metal cations such as Mg²⁺, Ca²⁺, Sr²⁺, Fe²⁺,Co²⁺, Mn²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺ and Pb²⁺ on the spectroscopic properties of the new fluoroionophore was investigated in acetonitrile-dichloromethane solution (9.5/0.5) by means of absorption and emission spectrometry. The blue shifts on the fluorescence spectrum were observed for all metal cations at 504nm. At the same time the fluorescence spectrum of the ligand showed quenching in the intensity of the signal at 504 nm for all metal cations except for Zn²⁺. Interaction of Co²⁺ with the ligand caused quenching of naphtyl fluorescence higher than 84%. The method showed good selectivity and sensitivity for Co²⁺ with respect to other metal cations with linear range and detection limit of 1.5 × 10⁻⁷ to 3.3 × 10⁻⁶M and 4.8 × 10⁻⁸M respectively.     

Complexation and DFT studies of lower rim hexahomotrioxacalix[3]arene derivatives bearing pyridyl groups with transition and heavy metal cations. Cone versus partial cone conformation

The binding of representative alkali, alkaline earth, transition and heavy metal cations by 2‐pyridylmethoxy derivatives (1b, in cone and partial cone conformations) of p‐tert‐butylhexahomotrioxacalix[3]arene was studied. Binding was assessed by extraction studies of the metal picrates from water into dichloromethane and by stability constant measurements in acetonitrile and methanol, using spectrophotometric and potentiometric techniques. Microcalorimetric studies of some selected complexes in acetonitrile were performed, as well as proton NMR titrations. Computational methods (density functional theory calculations) were also employed to complement the NMR data. The results are compared with those obtained with the dihomooxacalix[4]arene 2b and the calix[4]arene 3b derivative analogues. Partial cone‐1b is the best extractant for transition and heavy metal cations. Both conformers of 1b exhibit very high stability constants for soft and intermediate cations Pb²⁺, Cd²⁺, Hg²⁺, Zn²⁺ and Ni²⁺, with cone‐1b the strongest binder (ML, log β ≥ 7) and partial cone‐1b the most selective. Both derivatives show a slight preference for Na⁺. Besides the formation of ML complexes, ML₂ and M₂L species were also observed. The former complexes were, in general, formed with the transition and heavy metal cations, whereas the latter were obtained with Ag⁺ and Hg²⁺ and partial cone‐1b. In most cases, these species were corroborated by the proton NMR and density functional theory studies. Copyright © 2013 John Wiley & Sons, Ltd.     

Theoretical design on a new double functional device of 2,2′‐bipyridine‐embedded N‐(9‐pyrenyl methyl)aza‐15‐crown‐5

Theoretical design on a new molecular switch and fluorescent chemosensor double functional device of aza‐crown ether (2,2′‐dipyridine‐embedded N‐(9‐anthraceneyl(pyrenyl)methyl)aza‐15‐crown‐5) was explored. The interactions between ligands and a series of alkaline earth metal cations (Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺) were investigated. The fully optimized geometry structures of the free ligands ( L _1, L ₂) and their metal cation complexes ( L ₁/M²⁺, L ₂/M²⁺) were calculated with the B3LYP/6‐31G(d) method. The natural bond orbital analysis, which is based on optimized geometric structures, was used to explore the interaction of L ₁/M²⁺, L ₂/M²⁺ molecules. The absorption spectra of L _1, L ₂, L ₁/M²⁺, and L ₂/M²⁺, and their excited states were studied by time‐dependent density functional theory. A new type molecular device L ₂(2,2′‐dipyridine‐embedded N‐(9‐pyrenyl methyl)aza‐15‐crown‐5) is designed, which not only has the selectivity for Sr²⁺, and construct allosteric switch, but also has fluorescent sensor performance.     

Rhod-5N as a Fluorescent Molecular Sensor of Cadmium(II) Ion

The photophysical and complexing properties of Rhod-5N (commercially available) in MOPS buffer are reported. This fluorescent molecular sensor consists of a BAPTA chelating moiety bound to a rhodamine fluorophore. Its fluorescence quantum yield is low and a drastic enhancement of fluorescence intensity upon cation binding was observed. Special attention was paid to the complexation with Cd²⁺, a well known toxic metal ion. Possible interference with other metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, Pb²⁺) was examined. Rhod-5N was found to be highly selective of Cd²⁺ over those interfering cations except Pb²⁺. The limit of detection is 3.1 μg l⁻¹.     

Design and Synthesis of Highly Photostable Yellow–Green Emitting 1,8-Naphthalimides as Fluorescent Sensors for Metal Cations and Protons

Two highly photostable yellow–green emitting 1,8-naphthalimides 5 and 6, containing both N-linked hindered amine moiety and a secondary or tertiary cation receptor, were synthesized for the first time. Novel compounds were configured as “fluorophore–spacer–receptor” systems based on photoinduced electron transfer. Photophysical characteristics of the dyes were investigated in DMF and water/DMF (4:1, v/v) solution. The ability of the new compounds to detect cations was evaluated by the changes in their fluorescence intensity in the presence of metal ions (Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Co²⁺) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer leading to an enhancement in the dye fluorescence intensity. Compound 5, containing secondary amine receptor, displayed a good sensor activity towards metal ions and protons. However the sensor activity of dye 6, containing a tertiary amine receptor and a shorter hydrocarbon spacer, was substantially higher. The results obtained indicate the potential of the novel compounds as highly photostable and efficient “off–on” pH switchers and fluorescent detectors for metal ions with pronounced selectivity towards Cu²⁺ ions.     

Complex formation of pyridine‐azacrown ether amide macrocycles with proton and heavy metal ions in aqueous solution

This research concerns the analysis of the proton and metal ion binding of amide macrocycles of different structures and sizes by potentiometric, ¹H NMR and X‐ray diffraction methods. Protonated ligands exist as a 3D network structures. The ligands form 1:1 complexes with heavy metal ions (Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺, and Ni²⁺) in aqueous solutions and demonstrate the high selectivity towards Cu²⁺ cations. The pyridine‐2,6‐dicarbamide fragment provides structural rigidity to crown ether, resulting the molecule has an open cavity and faster kinetics of metal complexes formation. Copyright © 2015 John Wiley & Sons, Ltd.     

Zum Lumineszenzmodell manganaktivierter Titanate

The emission spectra and the temperature dependence of the relative intensity of luminescence of three manganese activated titanate phosphors [Zn₂TiO₄, (Mg, Zn)₂TiO₄, Mg₂TiO₄] after optical excitation with radiation from 300–500 nm were measured for various temperatures above 4,2 °K. The luminescence of the Mn⁴⁺-centre is influenced by the cations (Mg²⁺ or Zn²⁺) of the lattice. The temperature dependence of the relative intensity of the luminescence depends on the excitation wavelength. The results are discussed and found to be in good agreement with those of aC-C-model which assumes two energy parabolas for the excited state.     

A theoretical prediction on the ground‐state complexes bound by metal ions to thymine base isomers

Stability orderings of 150 stable complexes formed by metal ions (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺) and 13 stable thymine tautomers in both solvent and gas phases are obtained, and the optimal binding site for a metal ion in a specific thymine tautomer is identified. Results indicate that the complex with the canonical thymine tautomer (T1) is more stable than those with the rare ones, and the monodentate complex M–T1o4(o2) are their ground‐state form in the solvent phase. The ground‐state thymine complexes bound by Ca²⁺, Mg²⁺, or Zn²⁺ become bidentate M–T3o4lo2,n3, which is derived from a rare thymine tautomer T3o4l, whereas those bound by Na⁺ and K⁺ are still monodentate complexes M–T1o4(o2), however, in the gas phase. The differences in stability are discussed in detail from the binding strength of metal ions, relative energy of the corresponding thymine tautomers, and solution effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Novel Turn-on Fluorescence Probes for Al<Superscript>3+</Superscript> Based on Conjugated Pyrazole Schiff Base

One novel turn-on fluorescence probe founded on conjugated pyrazole Schiff base for detecting Al³⁺ was invented. The UV–vis and fluorescence spectrometer were employed to explore optical properties of this probe. The results got from those experiments indicated that this fluorescence probe manifested excellent sensitivity and selectivity for Al³⁺ compared with other cations examined(Ag⁺, Co²⁺, Mg²⁺, Cu²⁺, Ni²⁺, Pb²⁺,and Zn²⁺). In addition, this probe displayed a more rapid response and remained stable between pH 6 and 9 by investigating the fluorescence intensity under different response time and various pH values. Remarkably, the detection limit for Al³⁺ could lower to 1.0×10^?9M. Therefore, the probe could be potentially applied to the environment for the detection of Al³⁺, and the availability in biological range of pH that could be further studied to make this probe apply to biological systems in the future.     

A New Sensitive and Selective Off-On Fluorescent Zn<Superscript>2+</Superscript> Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted Dipyrromethene

3,3′,5,5′-Tetraphenyl-2,2′-dipyrromethene was described as a highly sensitive and selective Off-on fluorescent colorimetric chemosensor for Zn²⁺ based on the chelation-enhanced fluorescence (CHEF) effect. The reaction of dipyrromethene ligand with Zn²⁺ induces the formation of the [ZnL₂] complex, which exhibits the increasing fluorescence in 120 fold compared with ligand in the propanol-1/cyclohexane (1:30) binary mixture. The Zn²⁺ detection limit was 1.4 × 10^?7 М. The UV-Vis and fluorescence spectroscopic studies demonstrated that the dipyrromethene sensor was highly selective toward Zn²⁺ cations over other metal ions (Na⁺, Mg²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Cd²⁺ and Pb²⁺), excluding Hg²⁺.     

Comparison of Inductively Coupled Plasma with Classical Analytical Techniques in the Analysis of Southern Oregon Lithia Water: Inclusion of a Local Resource in the Undergraduate Chemistry Curriculum

Abstract

Lithia water, a community resource of local historical significance, is described as a central theme in the undergraduate analytical chemistry sequence. A statistical comparison of the classical determination of major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (HCO₃ ^?, Cl^?) reinforces statistical and charge‐balance concepts covered in analytical chemistry. Subsequent determination of these major cations by inductively coupled plasma (ICP) enables students to statistically evaluate the presence of bias between instrumental and classical methods. The effect of easily ionized elements on ICP calibration sensitivity and linearity via the use of cesium as an ionization suppressor is reported.     

Fluorescent and Chromogenic Receptor Bearing Amine and Hydroxyl Functionality for Iron (III) Detection in Aqueous Solution

The noncyclic 2,2′-[ethane-1,2-diylbis (iminomethanediyl)]diphenol (4) fluorescent receptor bearing two amine and hydroxyl groups have been designed and investigated for their binding properties towards various cations. The fluorescent spectral measurements revealed that receptor 4 is a selective fluorescent sensor for Fe³⁺ ions but not for metal ions such as Cr³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Bi³⁺. The binding ability was confirmed with spectroscopic methods and density functional theory calculation (DFT). This straightforward and cost effective receptor provides rapid detection of Fe³⁺ ions at concentrations as low as 2.5 μM and expected to be useful to design efficient chemically and biological sensor.     

Quinoline group grafted carbon nanotube fluorescent sensor for detection of Cu ion

A carbon nanotube-based fluorescent chemosensor MWNTs-glycine-N-8-quinolylamide (MWNTs-GNQ) has been designed and synthesized. Steady-state fluorescence emission studies showed that this material displays high selectivity and sensitivity for the Cu²⁺ ion over other cations such as Zn²⁺, Cd²⁺, Mg²⁺, Ca²⁺, and Ni²⁺.     

Mg substituted LiCoO2 for reversible lithium intercalation

A series of divalent non-transition metal, especially Mg doped LiCoO₂ solid solutions with the general formula LiMg_xCo_1−xO₂ (x=0.00–0.20) was synthesized by the solid state fusion method trying to reduce the cost and toxicity, and to improve the overall electrochemical cell performance. All synthesized cathodes were characterized by XRD, TG/DTA, FTIR, SEM, particle size analysis and charge-discharge performances at constant current of 0.05 mA. All compounds were found to possess phase purity, have better crystallinity, preferred surface morphology and size-reduced particles of uniform distribution. The incorporation of the larger Mg²⁺ ion compared to the Li⁺ ion up to 0.20 mol-% leads to an increase in the unit cell volume, which restricts the concentration of the Co-O bond upon delithiation. Mg²⁺, commonly known for its structure stabilizing effect, has been found to have only a small effect on the crystal lattice of LiCoO₂, especially at higher substituent levels, mainly due to the migration of Mg²⁺ ions from slab to inter-slab structure. The effect of Mg²⁺ on the modification of the capacity and structural stability compared to the unmodified LiCoO₂ cathode is discussed in detail.     

Optical properties of LiNbO3:Mg(5.21 mol %) and LiNbO3:Fe(0.009 mol %):Mg(5.04 mol %) crystals

Using methods of electronic spectroscopy, laser conoscopy, photoinduced (photoreactive) light scattering, and Raman light-scattering spectroscopy, we have studied the optical homogeneity, optical transmission, and photorefractive properties of single crystals LiNbO₃:Mg(5.21 mol %) and LiNbO₃:Fe(0.009 mol %):Mg(5.04 mol %) that were grown from congruent melts. We have ascertained that doping with “nonphotorefractive” Mg²⁺ cations causes suppression of the photorefractive effect in a lithium-niobate crystal. Upon double doping (Fe:Mg), if the concentration of Mg²⁺ cations exceeds the threshold concentration, the photorefractive effect is almost not observed and the presence of “photorefractive” Fe cations does not affect the photorefractive effect as strongly as in congruent crystals doped with Fe.