An efficient fluoroionophore for selective recognition of Hg and Cu ions

An azo-phenol based receptor 2 viz., 1-(6-nitrobenzothiazole-2-ylazo)naphthalene-2-ol has been designed, synthesized and characterized. The sensing behavior of receptor for different metal ions viz. Na⁺, K⁺, Ca²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Hg²⁺, Ag⁺ and Cd²⁺ has been studied in aqueous acetonitrile solution and was found specific for both the Hg²⁺ and Cu²⁺ transition metal ions. The chemosensor upon interaction with Hg²⁺ and Cu²⁺ ions shows well defined naked-eye visible color change from a yellow-green to pink and blue respectively, with a significant red-shift in absorption spectra. The estimated association constant and, enhancement and quenching in fluorescence emission spectra respectively, reveals the affinity of chemosensor for Hg²⁺ and Cu²⁺ ions. The FT-IR spectral analysis have suggested the probability of complexation, in the reaction medium, between metal ions and 2, through naphthol OH, azo N and thiazole N as a potential coordination sites.     

Effects of a site substitution of bivalent ions on Ag(Nb0.8Ta0.2)O3 ceramics

Bivalent ions equivalent substitution and equimolar substitution for Ag⁺ in silver niobate tantalate ceramic were studied, which will result in Ag_0.98A_0.01(Nb_0.8Ta_0.2)O₃ and Ag_0.98A_0.02 (Nb_0.8Ta_0.2)O₃ respectively, where A²⁺ = Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cu²⁺, Pb²⁺. The samples were synthesized by traditional solid method and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of a little Ag⁺ (in mol ratio 2 %) on the dielectric properties in Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cu²⁺, Pb²⁺ substituted samples, and the influences of radius and ionic electronegativity on the dielectric properties were discussed. The results showed that the substitution of most bivalent ions except large Ba²⁺ ions for a little Ag⁺ (in mol ratio 2 %) showed no obvious change on the perovskite structure and microstructure of Ag(Nb_0.8Ta_0.2)O₃ ceramics. Basically, the dielectric properties of equivalent substituted samples were better than that of equimolar equimolar substituted samples, Ca²⁺ equivalent substituted samples showed lower dielectric loss, and Cu²⁺ equivalent substituted samples showed higher dielectric constant.     

Enhancement of photocatalytic activity and stability of Ag2CO3 by formation of AgBr/Ag2CO3 heterojunction in mordenite zeolite

Two serious problems for semiconductor photocatalysts are their poor photocatalytic activity and low stability. In this work, Ag₂CO₃ nanoparticles incorporated in mordenite zeolite (MOR) by a facile precipitation method. Silver bromide (AgBr) with different weight percentage (20%, 40% and 50%) was coupled into Ag₂CO₃-MOR composite and producing a series of novel AgBr/Ag₂CO₃-MOR nanocomposites. The effects of AgBr on the Ag₂CO₃–MOR catalyst for the photocatalytic degradation of methyl blue (MB) under visible light irradiation have been investigated. The structure, composition and optical properties of nanocomposites were investigated by UV–Visible diffuse reflectance spectroscopy (UV–Vis DRS), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM). The prepared AgBr/Ag₂CO₃-MOR photocatalyst with the optimal content of AgBr (50 wt%) indicated higher photocatalytic activity than that of the Ag₂CO₃-MOR and Ag₂CO₃ for degradation of methylene blue (MB) under visible light irradiation. For studying of stability of nanocomposites, Fe⁺³ ions, as a cheap and available cocatalyst, was inserted into mordenite matrix (Fe³⁺/MOR) by impregnation method. The hybrid material (AgBr/Ag₂CO₃) was synthesized in the Fe³⁺/MOR matrix by precipitation method. The cycle experiments on the AgBr/Ag₂CO₃-Fe/MOR nanocomposite indicated that cocatalyst, not only to improve photocatalytic activity, but also enhance photoinduced stability of photosensitive silver compounds in all cycles with respect to MOR. On the basis of the experimental results, a possible mechanism for the enhanced photocatalytic activity and photoinduced stability of silver compounds by Fe³⁺ cocatalyst was proposed. The mordenite support played an important role in decreases of recombination of photogenerated electrons-holes and increases of MB absorption. The Fe cocatalyst reduced photocorrosion of silver compounds.     

Tuning photoluminescence of ZnS nanoparticles by silver

We report the results of investigation of the interaction of silver with presynthesized ZnS nanoparticles (NPs) that was stabilized by cetyl trimethyl ammonium bromide (CTAB). The photoluminescence properties of ZnS NPs were followed in the presence of Ag⁺ ions, Ag NPs and by the synthesis of Ag@ZnS core-shell nanoparticles. We observed that CTAB stabilized ZnS NPs emitted broadly in the region from 350–450 nm, when excited by 309 nm light. In the presence of Ag⁺ ions the emission peak intensity up to 400 nm was reduced, while two new and stronger peaks at 430 nm and 550 nm appeared. Similar results were obtained when Ag NPs solution was added to ZnS solution. However, when Ag@ZnS NPs were synthesized, the emission in the 350–450 nm region was much weaker in comparison to that at 540 nm, which itself appeared at a wavelength shorter than that of Ag⁺ ion added ZnS NPs. The observations have been explained by the presence of interstitial sulfur and Zn²⁺, especially near the surface of the nanocrystals and their interaction with various forms of silver. In addition, our observations suggest that Ag⁺ ions diffuse into the lattice of the preformed ZnS NPs just like the formation of Ag⁺ doped ZnS NPs and thus changes the emission characteristics. We also have pursued similar experiments with addition of Mn²⁺ ions to ZnS and observed similar results of emission characteristics of Mn²⁺ doped ZnS NPs. We expect that results would stimulate further research interests in the development of fluoremetric metal ion sensors based on interaction with quantum dots.     

Preparation of M metal/alumina-pillared mica composites (M = Cu, Ni) by in situ reduction of interlayer M ions of alumina-pillared fluorine micas

Alumina-pillared fluorine micas form micropores in the interlayer region and exhibit cation exchangeability. Reduction of 3d transition metal cations (Cu²⁺ and Ni²⁺) in the interlayer regions of the cation exchanged alumina-pillared micas was attempted using ethylene glycol or diethylene glycol. The Cu²⁺-exchanged pillared mica led to the formation of a pillared mica composite containing interlayer zero-valence Cu⁰ metal clusters along with Cu⁰ metal fine particles on external surfaces of pillared mica flakes when refluxed in either ethylene glycol or diethylene glycol. Ni²⁺ cations in the interlayer region were also found to be reducible by refluxing in diethylene glycol. The zero-valence metal contained in the refluxed products occurs in three forms: M⁰ clusters in the interlayer region, elongated fine particles sandwiched between silicate layers, and submicron spherical particles on external surfaces of mica crystals. The zero-valence metal/alumina-pillared mica composites thus obtained largely retained the micropore properties of the alumina-pillared micas.     

Photoluminescence properties and photocatalytic reactivities of Cu/zeolite and Ag/zeolite catalysts prepared by the ion-exchange method

Transition metal ions (Cu⁺, Ag⁺) incorporated within the cavities of zeolites by an ion-exchange method exhibit unique photoluminescence under UV irradiation due to the inner shell type electronic transition (d⁹s¹ → d¹⁰). Detailed photoluminescence investigations revealed that the transition metal ions exist in highly dispersed state with linear 2 coordination sphere and interact with NO_x (NO and N₂O) in their photoexcited states. In fact, Cu⁺ and Ag⁺ ions within zeolites show an efficient and unique photocatalytic performance for the decomposition of NO into N₂ and O₂ at ambient temperature. Detailed studies of the interaction of NO_x with the excited states of these metal ions indicated that an electron transfer from the s orbital of the excited state of Cu⁺ or Ag⁺ ions into the π^* antibonding orbital of NO_x initiates the decomposition of NO_x into N₂ and O₂.     

Ag and Dy doped zeolite as a broadband phosphor

Photoluminescence (PL) properties of silver (Ag) and dysprosium (Dy) codoped zeolites were investigated. It was found that PL from the ⁴F_9/2–⁶H_13/2 transition of Dy³⁺ ions at 575 nm is more than 50 times enhanced by the presence of Ag⁺ ions under ultraviolet excitation. The excitation wavelength dependence of the PL intensity coincided well with the absorption spectra of Ag⁺ ions, indicating that Dy³⁺ ions are excited by the energy transfer from Ag⁺ ions. In addition, by carefully optimizing annealing condition and Dy and Ag concentration, white light was realized due to the combination of blue emission of Ag⁺ ions, yellow emission of Dy³⁺ ions and red emission of Ag clusters.     

Controlled reduction of Cu to Cu with an N,O-type chelate under hydrothermal conditions to produce Cu2O nanoparticles

N,O-type organic chelates reduced coordinated Cu²⁺ ions under hydrothermal reaction conditions to produce Cu₂O/CuO nanoparticles. Chelates in which the N and O atoms are closely spaced produced smaller amounts of CuO nanoparticles, indicating their higher ability to reduce Cu²⁺ ions to Cu⁺ ions. [Cu(Gly)₂]² with the shortest ligand chain length produced only Cu₂O nanoparticles and, therefore, can be used as a single molecule precursor for the synthesis of Cu₂O nanoparticles.     

Formation and thermo-assisted stabilization of luminescent silver clusters in photosensitive glasses

Various photo-induced silver luminescent centres were obtained in photosensitive zinc and phosphate glasses containing silver ions after exposure to gamma or ultraviolet nanosecond pulsed-laser radiation. Gamma-irradiation of the glasses results mainly in the formation within the glass of electron-trapped and hole-trapped silver centres as evidenced by optical absorption, luminescence and electron spin resonance spectroscopies. For the highest irradiation doses silver clusters are obtained. Under ultraviolet nanosecond pulsed-laser exposure similar species are generated along the beam propagation direction as proven by the analogous optical and luminescence signatures. In this case for high irradiation doses few silver clusters are created. The evolution of the luminescence spectra with respect to the temperature and to the duration of the heat treatment after ultraviolet nanosecond pulsed-laser irradiation evidences the presence of potential barriers determining the stability limits of some species such as the Ag²⁺ hole-trapped centres or the Ag_m^x+ clusters composed of silver ions and silver atoms. A heat treatment of several hundreds of degrees is identified as a the key parameter for tailoring the optical properties and controlling the formation of Ag_m^x+ clusters in the photosensitive glasses.     

Electrochemical polymerization of benzene in the presence of Ag+, Pb2+ and Cu+ ions

Poly(p-phenylene) (PPP) films were synthesized by using benzene and fluorosulphonic acid (FSO₃H) as a strong acid containing Ag⁺, Pb²⁺ and Cu⁺ ions in methylene chloride (CH₂Cl₂) solution. Addition of Ag⁺ or Pb²⁺ ions into the polymerization medium improved the PPP films formation, but Cu⁺ ion did not have an effect on polymerization. PPP films were characterized by cyclic voltammetry, IR and TGA. Dry conductivities were measured by using four probe technique. Received: 18 September 2000 / Reviewed and accepted: 20 September 2000     

Bactericidal effects of different silver-containing materials

The evaluation of the bactericidal effect of different silver-containing materials where silver is available as Ag⁺ (silver nitrate and different silver-exchanged zeolites), as metallic Ag⁰ (commercial silver nanoparticles) or as oxide (silver (I) oxide) was carried out in order to elucidate the importance of the bioavailability of silver (i.e., as free ions, metallic particles, combination of them, clusters, complexes, partially soluble or insoluble salts, etc.) on its bactericidal action.For the different materials tested, their bactericidal effect is ordered in the following sequence: AgNO₃ > Ag-ZSM-5 > Ag₂O > commercial silver-exchanged zeolite (granular) > commercial silver-exchanged zeolite (pellets) > Ag nanoparticles. In general, as the content of bioavailable ionic silver increases, the biocidal effectiveness of the corresponding silver-releasing material increases too.     

Silver-embedded zeolite crystals as substrates for surface-enhanced Raman scattering

This paper reports the preparation of a type of Ag-embedded zeolite crystals as surface-enhanced Raman spectroscopy (SERS) substrates by chemical reduction of Ag⁺-exchanged ZSM-5. Ag⁺ ions were loaded into the zeolite framework by ion exchange. Then the exchanged-Ag⁺ ions were reduced and metallic silver clusters formed inside the zeolite channel. The resulting Ag-embedded zeolite crystals are characterized by using a number of techniques including X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm silver formed inside the crystal channel. The fabricated Ag-embedded ZSM-5 zeolite substrates displayed strong and reproducible SERS activity for different Raman probe molecules such as Tris(2,2′-bipyridyl) ruthenium(II) chloride (RuBpy) and rhodamine 6G (R6G). Since silver embedded into the zeolite channel without changing the crystal surface property, the Ag–ZSM-5 zeolite crystal can be used to prepare different SERS-active substrate (SERS-tags), in which different probe molecules may be detected. Such Ag-embedded zeolite substrate would be useful in chemical and biological sensing and in the development of SERS-based analytical devices.     

Modification of algae with zinc,copper and silver ions for usage as natural composite for antibacterial applications

Nanometer sized metal particles are used in many applications as antimicrobial materials. However in public discussion nanoparticular materials are a matter of concern due to potential health risks. Hence there is a certain demand for alternative antimicrobial acting materials. For this, the aim of this work is to realize an antimicrobial active material based on the release of metal ions from a natural depot. By this, the use of elemental metal particles or metal oxide particles in nanometer or micrometer scale is avoided. As natural depot four different algae materials (gained from Ascophyllum nodosum, Fucus vesicolosus, Spirulina platensis and Nannochloropsis) are used and loaded by bioabsorption with metal ions Ag⁺, Cu^2 + and Zn^2 +. The amount of metal bound by biosorption differs strongly in the range of 0.8 to 5.4 mg/g and depends on type of investigated algae material and type of metal ion. For most samples a smaller release of biosorbed Ag⁺ and Cu^2 + is observed compared to a strong release of Zn^2 +. The antibacterial activity of the prepared composites is investigated with Escherichia coli. Algae material without biosorbed metal has only a small effect on E. coli. Also by modification of algae with Zn^2 + only a small antibacterial property can be observed. Only with biosorption of Ag⁺, the algae materials gain a strong bactericidal effect, even in case of a small amount of released silver ions. These silver modified algae materials can be used as highly effective bactericidal composites which may be used in future applications for the production of antimicrobial textiles, papers or polymer materials.     

Aspects of the in vitro bioactivity and antimicrobial properties of Ag+- and Zn2+-exchanged 11 Å tobermorites

11 Å tobermorite, Ca₅Si₆O₁₆(OH)₂ · 4H₂O, is a layer lattice ion exchange mineral whose potential as a carrier for Ag⁺ and Zn²⁺ ions in antimicrobial, bioactive formulations has not yet been explored. In view of this, the in vitro bioactivity of Ag⁺- and Zn²⁺-exchanged 11 Å tobermorites and their bactericidal action against S. aureus and P. aeruginosa are reported. The in vitro bioactivity of the synthetic unsubstituted tobermorite phase was confirmed by the formation of bone-like hydroxycarbonate apatite (HCA) on its surface within 48 h of contact with simulated body fluid. The substitution of labile Ag⁺ ions into the tobermorite lattice delayed the onset of HCA-formation to 72 h; whereas, the Zn²⁺-substituted phase failed to elicit an HCA-layer within 14 days. Both Ag⁺- and Zn²⁺-exchanged tobermorite phases were found to exhibit marked antimicrobial action against S. aureus and P. aeruginosa, two common pathogens in biomaterial-centred infections.     

Optical properties of aluminophosphate glasses containing silver, tin, and dysprosium

The spectroscopic properties of a Dy³⁺-doped aluminophosphate glass containing silver and tin were reported. Different oxidation and aggregation states of silver were obtained by varying silver concentration and glass thermal history. The addition of silver and tin at the lowest concentration studied results in Dy³⁺ ions emission under nonresonant UV excitation in connection with the appearance of an excitation band around 270 nm, which is associated to isolated Ag⁺ ions and twofold-coordinated Sn centers. The increase in silver and tin concentration leads to a broadening of aforementioned band and to the presence of charged silver dimers as evidenced by the appearance of an excitation band around 330 nm. The data indicated that light absorption might take place at ionic silver species and twofold-coordinated Sn centers, followed by energy transfer to Dy³⁺ ions. After heat treatment, ionic silver species were reduced to atomic Ag by tin with the subsequent formation of Ag nanoparticles (NPs) inside the dielectric host. A quenching effect in Dy³⁺ ions luminescence was shown with the presence of the Ag NPs, most notably for excitation of ⁶H_15/2 → ⁴F_9/2, ⁴I_15/2, ⁴G_11/2 transitions, which were in resonance with the dipole absorption mode of the particles. The silver NPs were believed to provide radiationless pathways for excitation energy loss in Dy³⁺ ions.     

Synthesis of nanoparticles composed of silver and copper for metal–metal bonding

A metal–metal bonding technique is described that uses nanoparticles composed of silver and copper. Colloid solutions of nanoparticles with an Ag content of 0–100?mol% were prepared by simultaneous reduction of Ag⁺ and Cu²⁺ using hydrazine with polyvinylpyrrolidone and citric acid as stabilisers. The nanoparticles ranged in size from 34 to 149?nm depending on the Ag content. Copper discs were strongly bonded at 400°C for 5?min under 1.2?MPa pressure in hydrogen gas; the maximum shear strength was as high as 23.9?MPa. The dependence of shear strength on the Ag content was explained by a mismatch between the d-spacings of Cu metal and Ag metal.     

Surface engineered magnetic nanoparticles for removal of toxic metal ions and bacterial pathogens

Surface engineered magnetic nanoparticles (Fe₃O₄) were synthesized by facile soft-chemical approaches. XRD and TEM analyses reveal the formation of single-phase Fe₃O₄ inverse spinel nanostructures. The functionalization of Fe₃O₄ nanoparticles with carboxyl (succinic acid), amine (ethylenediamine) and thiol (2,3-dimercaptosuccinic acid) were evident from FTIR spectra, elemental analysis and zeta-potential measurements. From TEM micrographs, it has been observed that nanoparticles of average sizes about 10 and 6 nm are formed in carboxyl and thiol functionalized Fe₃O₄, respectively. However, each amine functionalized Fe₃O₄ is of size ∼40 nm comprising numerous nanoparticles of average diameter 6 nm. These nanoparticles show superparamagnetic behavior at room temperature with strong field dependent magnetic responsivity. We have explored the efficiency of these nanoparticles for removal of toxic metal ions (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Pb²⁺ and As³⁺) and bacterial pathogens (Escherichia coli) from water. Depending upon the surface functionality (COOH, NH₂ or SH), magnetic nanoadsorbents capture metal ions either by forming chelate complexes or ion exchange process or electrostatic interaction. It has been observed that the capture efficiency of bacteria is strongly dependent on the concentration of nanoadsorbents and their inoculation time. Furthermore, these nanoadsorbents can be used as highly efficient separable and reusable materials for removal of toxic metal ions.     

Recovery of 137Cs, 90Sr, 90Y, and d-element ions from aqueous solutions with sorbents containing triethylenediamine

The possibility of using sorbents based on KSKG coarsely porous silica gel and containing triethylenediamine N(CH₂-CH₂)₃N (TEDA) for recovering ¹³⁷Cs, ⁹⁰Sr, ⁹⁰Y, and d-element ions (Cu²⁺, Ni²⁺) from aqueous solutions was examined. Both ⁹⁰Sr, ⁹⁰Y radionuclides and Cu²⁺, Ni²⁺ ions are sorbed on KSKG containing 0.01–6.72 wt % TEDA. However, on sorbents based on KSKG and containing complexes of Cu²⁺, Ni²⁺, and Zn²⁺ nitrates with TEDA, the ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y radionuclides are not sorbed. The equilibrium in the systems with these sorbents is attained within 3 h. The sorption capacity for Cu²⁺ and Ni²⁺ strongly depends on the conditions of the sorbent synthesis. The capacity of the sorbents for Cu²⁺ varies from 63 to 320 mg of metal per gram of sorbent. For Ni²⁺, the sorption capacity is considerably lower (no more than 130 mg of Ni²⁺ per gram of sorbent). The distribution coefficients of ⁹⁰Sr and ⁹⁰Y are 300–700 ml g^?1 at the contact time of the solid and liquid phases of 96 h and V/m = 100 ml g^?1.     

Construction of Cuprous Oxide Electrodes Composed of 2D Single‐Crystalline Dendritic Nanosheets

An unusual anisotropic growth of Cu₂O is stabilized via the electrochemical synthesis of Cu₂O in the presence of Ag⁺ ions, which results in the formation of Cu₂O electrodes composed of 2D sheetlike crystals containing complex dendritic patterns. It is quite unusual for Cu₂O to form a 2D morphology since it has a 3D isotropic cubic crystal structure where the a, b, and c axes are equivalent. Each Cu₂O sheet is single‐crystalline in nature and is grown parallel to the {110} plane, which is rarely observed in Cu₂O crystal shapes. A various set of experiments are performed to understand the role of Ag⁺ ions on the 2D growth of Cu₂O. The results show that Ag⁺ ions are deposited as silver islands on already growing Cu₂O crystals and serve as nucleation sites for the new growth of Cu₂O crystals. As a result, the growth direction of the newly forming Cu₂O crystals is governed by the diffusion layer structure created by the pre‐existing Cu₂O crystals, which results in the formation of 2D dendritic patterns. The thin 2D crystal morphology can significantly increase the surface‐to‐volume ratio of Cu₂O crystals, which is beneficial for enhancing various electrochemical and photoelectrochemical properties of the electrodes. The photoelectrochemical properties of the Cu₂O electrodes composed of 2D dendritic crystals are investigated and compared to those of 3D dendritic crystals. This study provides a unique and effective route to maximize the {110} area per unit volume of Cu₂O, which will be beneficial for any catalytic/sensing abilities that can be anisotropically enhanced by the {110} planes of Cu₂O.     

Magnetic nanoparticles/graphitic carbon nanostructures composites: Excellent magnetic separable adsorbents for precious metals from aqueous solutions

A facile, low-cost and high-yield route was used for synthesis of magnetic nanoparticles/graphitic carbon nanostructures (MNPs/GCNs) adsorbents with adjustable GCNs structues, in which the cheap ion-exchanged resins and iron salts were adopted as the precursors. The synthesized MNPs/GCNs composites could be used as effective mobile adsorbents for removal of precious metal ions (Ag⁺ and Au³⁺). The adsorption quantity of the adsorbents for Ag⁺ and Au³⁺ ions is up to 7.88 mg/g and 7.92 mg/g, respectively, which is much higher than that of activated carbon. Notably, the adsorbents could be easily separated from solution with a commercial magnet due to the magnetic property, which is very beneficial to their practical application. The kinetics for Ag⁺ and Au³⁺ ions adsorption on MNPs/GCNs composites followed the pseudo-second-order kinetics. The XPS analyses demonstrated that the adsorbed Ag⁺ and Au³⁺ ions exsited in the form of the zero valence state silver and gold, respectively.