Zn2+-Schiff’s Base Complex as an “On–Off-On” Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff’s base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H₂L) and its metal complexes with Zn²⁺, Cu²⁺ and Ag⁺ ions. This study aims to investigate the behavior of H₂L and the binuclear Zn²⁺ complex (1) as fluorescent probes for the detection of metal ions (Zn²⁺, Cu²⁺ and Ag⁺) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H₂L ligand were optimized using the B3LYP/6–311?+??+?G** level of theory, while the L^?2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6–311?+??+?G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6–311?+??+?G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn²⁺, Cu²⁺ and Ag⁺). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag⁺ and Cu²⁺ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch “On–Off-On” via the replacement of Cu²⁺ by Ag⁺ ions, as proved experimentally.

     

Manipulation of optical properties of Ag/Cu alloy nanowire arrays embedded in anodic alumina membranes

Arrays of Ag/Cu alloy nanowires embedded in anodic alumina membranes (AAMs) were synthesized by directly electrodepositing from a mixing electrolyte solution containing Ag⁺ and Cu²⁺ ions. Manipulations of optical properties of the resulting samples were successfully achieved by tuning the molar ratio of Ag⁺ and Cu²⁺ ions in the starting materials. When the ratio is less than 2:20, two surface plasma resonance (SPR) peaks corresponding to Ag and Cu appear, respectively. After annealing treatment, the SPR peak corresponding to Cu disappears, and that of Ag presents a red shift. Furthermore, this red shift can be up to 85 nm when the molar ratio of Ag⁺ and Cu²⁺ reduce to 1:20, which is attributed to the transferable electrons from Cu atoms.     

Preparation of Cu2O nanowires by thermal oxidation-plasma reduction method

Facial synthesis of cuprous oxide (Cu₂O) nanowires by directly heating copper substrates is difficult; however, in this study, it was successfully done by thermal oxidation followed by a plasma reduction process. The preparation of CuO nanowires with an average diameter of 76.2?nm supported on the surface of copper substrate was conducted first in air at 500?°C for 3?hrs, and then the CuO nanowires were reduced into Cu₂O in 15?min using either radio frequency (RF) N₂ plasma or microwave (MW) N₂ plasma. The characteristics of CuO and Cu₂O nanowires were analyzed using XRD, FE-SEM, and TEM. The results showed that Cu₂O nanowires can be successfully reduced from CuO nanowires by a simple, promising, and fast nitrogen plasma process. Moreover, in RF plasma, narrower and longer Cu₂O nanowires can be produced as compared to MW plasma, because energetic N-containing species can reduce the nanowires at a relatively lower temperature.     

Electrical contact properties of Cu2S nanowires grown vertically on Cu foil by gas–solid reaction

We grew Cu₂S nanowires vertically on Cu foil by gas–solid reaction with a gas mixture of O₂ and H₂S. The electrical contact properties between the Cu₂S nanowires and Cu foil were investigated using a modified current–voltage–temperature plot. The Cu/Cu₂S layer exhibited the characteristics of a Schottky barrier with a barrier height of ∼0.72 eV, which was closer to the value for Cu/Cu₂O than to Cu/Cu₂S. Energy dispersive spectroscopy results showed the presence of Cu-oxide between the Cu₂S nanowires and Cu foil. The overall structure was Cu/Cu-oxide/Cu₂S and the electrical properties were controlled by the Cu/Cu-oxide.     

Features of the absorption spectra of thin films of M 2Ag1 − x CuxI3 solid solutions (M = Rb, Cs)

The absorption spectra of thin films of (MI)_{1 ? y} (Ag_{1 ? x} Cu_xI)_y solid solutions (M = Rb, Cs) with the initial molar concentration y = 0.33 have been investigated. It is established that, at low concentrations x, a local exciton band due to Cu⁺ ions is split off from the main long-wavelength exciton bands. In Rb₂Ag_{1 ? x} Cu_xI₃ solutions, the concentration shift of exciton bands indicates the formation of a persistent-type exciton spectrum. However, in Rb₂Ag_{1 ? x} Cu_xI₃ with x ≥ 0.5 and in Cs₂Ag_{1 ? x} Cu_xI₃ with x > 0.2, exciton spectra of amalgamation type are observed, which are related to the formation of more stable M ₃Ag_{2 ? 2x} Cu_2x I₅ solid solutions. The formation of these solutions leads to broadening of the exciton bands and to the concentration transition from persistent-to amalgamation-type exciton spectra.     

Oleylamine‐Assisted Phase‐Selective Synthesis of Cu2−xS Nanocrystals and the Mechanism of Phase Control

Environmentally friendly Cu_2?x S compounds exist in many different mixed phases in nature, while their nanoscale counterparts can be pure phase with interesting localized surface plasmon resonance properties. Because of the complexity of composition and phase, controllable synthesis of Cu_2?x S nanocrystals becomes an important scientific issue in colloidal chemistry. In this work, a hot‐injection method is developed to synthesize Cu_2?x S nanocrystals by injecting a sulfur precursor into a copper precursor using oleylamine and octadecene as solvents. By varying the reaction parameters (temperature, volume ratio of oleylamine/octadecene, molar ratio of Cu/S in the precursors), hexagonal CuS, monoclinic Cu_1.75S, and rhombohedral Cu_1.8S, nanocrystals can be selectively synthesized, providing a platform to illustrate the mechanism of crystal phase control. The crystal phase control of Cu_2?x S nanocrystals is oleylamine‐determined by controlling the molar ratio of Cu/S in the reaction precursors as well as the ratio of Cu_2?x S clusters/Cu⁺ in the subsequent reaction. More importantly, temperature plays an important role in varying the molar ratio of Cu/S and Cu_2?x S clusters/Cu⁺ in the reaction system, which significantly influences the crystal phase of the resulting Cu_2?x S nanocrystals. The understanding into crystal control provides a guideline to realize reproducible phase‐selective synthesis and obtain well‐defined high‐quality materials with precise control.     

A Pyrene-based Highly Selective Turn-on Fluorescent Sensor for Copper(II) Ion and its Application in Live Cell Imaging

A new pyrene derivative (chemosensor 1) containing a picolinohydrazide moiety exhibits high selectivity for Cu²⁺ ion detection in mixed aqueous media (CH₃OH:H₂O = 7:3). Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu²⁺. However, the metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Fe²⁺, Fe³⁺, Hg²⁺, K⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ produced only minor changes in fluorescence for the system. The apparent association constant (K _a) of Cu²⁺ binding in chemosensor 1 was found to be 2.75*10³ M⁻¹. The maximum fluorescence enhancement caused by Cu²⁺ binding in chemosensor 1 was observed over the pH range 5–8. Moreover, by means of fluorescence microscopy experiments, it is demonstrated that 1 can be used as a fluorescent probe for detecting Cu²⁺ in living cells.     

Self‐Assembly of Ag6 Clusters into Nanowires for Nonenzymatic Electrochemical Sensing of Glucose

Self‐assembly of metal nanoclusters into 3D ordered superstructures and the exploration of their electrochemical properties are highly significant for fundamental research and practical application. In this study, atomically precise Ag₆(NALC)₅ nanoclusters are successfully synthesized and their structure is determined carefully. It is interesting that the prepared Ag₆(NALC)₅ nanoclusters can be self‐assembled into ultrafine nanowires, long ribbons, and finally 3D porous network in the mixed solution of water and ethanol, which can be attributed to the solvent polarity, static electricity interaction between ligands, and the possible Van der Waals attractions. Such assembly phenomenon lays a foundation for the future fabrication of silver clusters‐based nanodevices. In addition, the synthesized silver nanoclusters can be used for electrochemical sensing of glucose with high detection sensitivity, selectivity, and low limit of detection. This work is expected to be helpful for the synthesis of atomically precise metal nanoclusters and their applications in fabrication of nanodevices for chemical sensors.     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

Ternary alloying effect on the melting of metal clusters

Canonical ensemble Monte Carlo simulations are applied to investigate the melting of the icosahedral 55-atom Ag-Cu-Au clusters. The clusters are modeled by the second-moment approximation of the tight-binding (TB-SMA) many-body potentials. Results show that the introduction of the only Cu atom of the third alloying metal in the bimetallic Ag₄₃Au₁₂ cluster, forming the Ag₄₂Cu₁Au₁₂ cluster, can greatly increase the melting point of the cluster by about 100 K. It is also found that the substitution of the only Cu atom of the third alloying metal in the Ag₁Au₅₄ clusters, forming the Ag₁Cu₁Au₅₃ cluster, can result in an increase of 40 K in the melting point. It can be concluded that the melting points of the bimetallic clusters can be tuned by the third metal impurities doping. In addition, the surface segregation of Ag atoms in the Ag-Cu-Au trimetallic clusters occurs even after melting.     

Evaluating the electric property of different crystal faces and enhancing the Raman scattering of Cu2O microcrystal by depositing Ag on the surface

The surface electric property of Cu₂O microcrystal affects the interaction of facets with substance in the aqueous solution, and hence plays a key role in determining the photocatalytic activity. In this paper, the capability of Cu₂O microcrystals with exclusive {111}, {110} or both lattice surfaces in reducing Ag⁺ to Ag⁰ were investigated. Ag particles selectively deposited on {111} surfaces of Cu₂O, while not on {110} surfaces. The different behaviors of the two surfaces are mainly attributed to their different electric properties: negatively-charged {111} surfaces absorb Ag⁺ ions while positively-charged {110} surfaces repel them. Raman scattering of Cu₂O {111} surfaces was enhanced by the photo-deposition of Ag particles.     

Synthesis and electrochemical characterization of M2Mn3O8 (M = Ca,Cu) compounds and derivatives

M₂Mn₃O₈ (M = Ca²⁺, Cu²⁺) compounds were synthesized and characterized in lithium cells. The M²⁺ cations, which reside in the van der Waals gaps between adjacent sheets of Mn₃O₈⁴⁻, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li⁺/Cu₂Mn₃O₈ may be inserted electrochemically, with concomitant reduction of Cu²⁺ to Cu metal, but less Li can be inserted into Ca₂Mn₃O₈. In the case of Cu²⁺, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu⁺ rather than Cu²⁺ and Li⁺/Cu⁺ exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4 Li⁺/Cu₂Mn₃O₈ can be cycled reversibly. The unusual mobility of + 2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M²⁺ intercalation compounds.     

Phase transitions in CuS–Ag2S nanoparticle system

(Ag₂)_xCu_1?xS, x = .2, .4, .6 and .8 nanoparticles were synthesized by the solvothermal method. The as-synthesized nanoparticles were characterized by X-ray diffraction to study the crystal structure and size. The surface morphologies of the above samples were studied using scanning electron microscope. As there is continuous shift in the lower wavelength absorption edge of the UV–VIS spectrum of these samples with concentration, (Ag₂)_xCu_1?xS nanoparticles can be tuned to different band gap energies by varying the composition. The D.C. electrical resistance was measured in the temperature range 310–485 K. As Ag₂S transforms from monoclinic to bcc at around 450 K, copper sulfide nanoparticles also shows a phase transition at around 470 K, the effects of these two transitions are seen in the resistance measurements and in the UV–VIS spectra of the entire system. The electrical resistance of (Ag₂)_xCu_1?xS nanoparticles rapidly reduces as more and more copper sulfide is added.     

The effect of Ag substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor that crystallizes in the simple cubic structure at room temperature. Structural transitions above and below room temperature are accompanied by step-like changes in electrical conductivity. The substitution of Ag⁺ for Cu⁺ in Cu₇PSe₆ stabilized the simple cubic structure over a wider range of temperatures than is observed for the pure compound. A disproportionate decrease in electrical conductivity accompanies modest levels of silver substitution. The prominent step in electrical conductivity associated with the low-temperature crystallographic phase transition disappears in (Ag_xCu_1−x)₇PSe₆ solid solutions for a composition parameter x=0.20, replaced by two distinct changes in the slope of conductivity below room temperature.     

PAC study of ionic motion in silver compound superionic conductors

Ionic motion in superionic conductors, Ag₂S, Ag₂Se and Ag₃SI was investigated by γ-γ PAC on¹¹¹Cd. Diffusion constant measurements showed that probe ions migrate almost as fast as Ag⁺ ions above 500K in Ag₂S and Ag₂Se and above 700K in Ag₃SI. Multivalent impurities were found to be unstable in AgI and Ag₂Te. The correlation time of ionic motion was deduced from the observed relaxation rate together with the diffusion constants. The correlation time and its activation energy increase in order of Ag₂S, Ag₂Se and Ag₃SI.The flight distance of Ag⁺ ions remains almost constant in the measured temperature range.     

Controlled Cu content of electrodeposited CoCu nanowires through pulse features and investigations of microstructures and magnetic properties

CoCu alloy nanowire arrays embedded in anodic alumina template were fabricated by ac pulse electrodeposition. Different off-times between pulses in an electrolyte with constant concentration of Co⁺² and Cu⁺² and acidity of 4 were employed. The effect of deposition parameters on the alloy contents, microstructures and magnetic properties of Co_xCu_1−x nanowires were studied. It is shown that Co content decreased by increasing the off-time between pulses in a wide range (x = 0.53-0.07). These results are in consistence with saturation magnetization, which was reduced with increase in the off-time between pulses. It was also found that by optimizing the off-times, it is possible to fabricate CoCu nanowires with mixed phase of hcp Co, fcc Cu and fcc CoCu crystal phase.     

Experimental evidence for the Onsager reciprocal relation in mixed conduction

The cross conductivities in the ionic-electronic conduction have been measured for α Ag₂Se at 162°C and β Cu₂S at 340°C, and it has been found that the Onsager reciprocal relation is satisfied in the whole measured range of the nonstoichiometry. The measured cross conductivities are smaller than the ionic conductivity by the factor 10^?2 to 10^?3.     

197Au and125Te Mössbauer spectroscopic study on the low temperature phases of Ag3AuX2 (X=S,Se, and Te)

¹⁹⁷Au and¹²⁵Te Mössbauer spectroscopy has been applied for the low-temperature β-phases of Ag₃AuX₂ (X=S, Se, and Te). The values of I. S. and Q. S. for¹⁹⁷Au suggest that the gold atoms, linearly coordinated by two chalcogen atoms in these phases, exist as monovalent cations. The¹²⁵Te Mössbauer spectra suggest that the tellurium atoms are substantially ionic for both Ag₂Te and Ag₃AuTe₂. The nature of X-Au-X bonds is discussed on the basis of the Mössbauer data and the bond distances.     

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th–13th century)

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag⁺, Cu⁺ and Cu²⁺ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag⁺ and Cu⁺ ions can be present. The achievement of metallic Cu and the absence of Cu²⁺ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.     

The microwave conductivity of solid electrolytes

We investigate the frequency dependent conductivity σ(ω) for ω in the vicinity of the jump rate Γ₀. The most general model based on hopping diffusion predicts a σ(ω) consistent with experiment for β-Al₂O₃ but qualitatively at odds for Ag⁺ and Cu⁺ conductors. We consider the coupling of the transition rate to an external variable such as a long lived, low frequency lattice mode and show that this mechanism can give structure in σ(ω) of the form observed in Ag⁺ and Cu⁺ conductors.