Preparation of thermo-responsive electrospun nanofibers containing rhodamine-based fluorescent sensor for Cu<Superscript>2+</Superscript> detection

A series of Cu²⁺-sensing nanofibers has been successfully prepared by electrospinning of poly[(N-isopropylacrylamide)-co-(N-hydroxymethyl acrylamide)-co-(4-rhodamine hydrazonomethyl-3-hydroxy-phenyl methacrylate)] [poly(NIPAAm-co-NMA-co-RHPMA), PNNR] random copolymers. These PNNR copolymers were synthesized by free radical copolymerization of three monomers, thermo-responsive NIPAAm, chemically crosslinkable NMA and Cu²⁺-sensing RHPMA, with the composition of RHPMA in the range of 2.4–16.3 wt%. In acidic environments, the PNNR copolymers showed highly selective and sensitive recognition and displayed “ON-OFF” fluorescence toward Cu²⁺ both in solution and in solid state (thin films and nanofibers). From the quantitative analysis via Stern-Volmer plots, PNNR nanofibers exhibited comparable Stern-Volmer constants as those of PNNR solutions in the order of 10⁴ M^?1, which are much higher than those of PNNR thin films. The enhanced sensitivity of PNNR electrospun nanofibers is attributed to their higher surface area compared to dip-coating films. The PNNR nanofibers also exhibited an on/off switchable sensing behavior in response to temperature change due to the hydrophilic-hydrophobic transition of PNIPAAm. In addition, the binding of PNNR with Cu²⁺ is chemically reversible both in solution and in nanofibers with the treatment of Na₄EDTA.     

Synthesis and characterization of CMC/MMT nanocomposite for Cu<Superscript>2+</Superscript> sequestration in wastewater treatment

Organic–inorganic hybrid nanocomposites are promising materials for remediation of pollutants from wastewater, as they exhibit the unique characteristics of both inorganic and organic materials. In this study, carboxymethyl cellulose/montmorillonite Nanocomposite (CMC/MMT-NC) was prepared and applied for Cu²⁺ sequestration. CMC/MMT-NC was characterized by FTIR and SEM before and after the sequestration process, indicating fundamental changes in surface morphology after treatment experiments. The parameters affecting the process such as pH, contact time, CMC/MMT-NC mass, Cu²⁺ concentration and temperature were experimentally adjusted. Statistical regression variables (R², RMSE, RSS, F-Value and P-Value) were calculated to predict the best-applied isotherm, kinetic and thermodynamic modeling. Freundlich isotherm model successfully described the equilibrium data, which implies a multilayer adsorption process. Kinetic results were well fitted to pseudo-second-order kinetic model. Intraparticle diffusion (IPD) model showed the control of the boundary layer moreover, IPD model cannot be accepted as the only rate-determining step. The apparent activation energy (Ea) was 35.65 kJ/mol, which revealed a physisorption process. The thermodynamic study in means of ΔG⁰, ΔH⁰, and ΔS⁰ demonstrated the feasibility, spontaneity and exothermicity of Cu²⁺ sequestration. Application study confirmed the efficiency of CMC/MMT nanocomposite to remediate Cu²⁺ from synthetic and natural polluted seawater.     

Optimization of Opto-Electrical and Photocatalytic Properties of SnO<Subscript>2</Subscript> Thin Films Using Zn<Superscript>2+</Superscript> and W<Superscript>6+</Superscript> Dopant Ions

Abstract  

A series of Zn²⁺ and W⁶⁺ doped tin oxide (SnO₂) thin films with various dopant concentrations were prepared by spray pyrolysis deposition, and were characterized by X-ray diffraction, atomic force microscopy, contact angle, absorbance, current density–voltage (J–V) and photocurrent measurements. The results showed that W⁶⁺ doping can prevent the growth of nanosized SnO₂ crystallites. When Zn²⁺ ions were used, the crystallite sizes were proved to be similar with the undoped sample due to the similar ionic radius between Zn²⁺ and Sn⁴⁺. Regardless of the dopant ions’ type or concentration, the surface energy has a predominant dispersive component. By using Zn²⁺ dopant ions it is possible to decrease the band gap value (3.35 eV) and to increase the electrical conductivity. Photocatalytic experiments with methylene blue demonstrated that with zinc doped SnO₂ films photodegradation efficiencies close to 30% can be reached.     

Cu<Superscript>2+</Superscript> adsorption onto ion-imprinted composite hydrogels: thermodynamics and mechanism studies

In the current study, in situ free radical polymerization was employed to prepare Cu²⁺-imprinted composite hydrogel (Cu²⁺-ICH). The cross-sectional morphology of the Cu²⁺-ICH evaluated by scanning electron microscopy indicated that the copper-loaded Cu²⁺-ICH became rougher and the pore size of the gel became smaller compared to the unloaded Cu²⁺-ICH. The ability of the Cu²⁺-ICH to adsorb Cu²⁺ from aqueous solutions was assessed using batch adsorption technique. The adsorption capacity increased with the initial concentration of Cu²⁺, but decreased as the temperature rose from 298 to 318 K. Thermodynamic parameters such as Gibbs free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) for the Cu²⁺ adsorption were evaluated. It was suggested that the adsorption process was a spontaneous, exothermic process that had positive entropy. Selectivity study indicated that ion imprinting technique resulted in excellent affinity of the Cu²⁺-ICH toward Cu²⁺. Finally, the adsorption mechanism was studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results indicated that copper adsorption was mainly through interactions with the amine and carbonyl groups.     

A Chiral Salen-type Schiff Base Cu<Superscript>2+</Superscript> Complex for the Vinylic-type Polymerization of Norbornene

Abstract  

The chiral Salen-type Schiff base ligand H ₂ L (H ₂ L = (s)-(+)2,2′-bis(2-hydroxy-3-methoxybenzylideneamino)-1,1′-binaphthyl), was selected to obtain the new chiral Cu²⁺ complex CuL (1), which was found to catalyze the polymerization of norbornene (NBE). The complex shows the distinctively distorted geometry from a square-planar reactive center, this feature being suggested to account for the efficient catalysis on the vinylic-type polymerization of NBE, with moderate molecular weights and narrow molecular weight distributions.     

Study IR spectroscopic study of sorption of Cu<Superscript>2+</Superscript> ions on granulated chitosan

Formation of insoluble compounds, in particular, the basic salt (CuOH)₂SO₄ and copper hydroxide, is a side process that reduces the concentration of copper ions in the solution and causes overstatement of the data on sorption. Formation of chitosan sulfate salt is a competing side process. Side processes and the structural inhomogeneity of chitosan and the sorption products obtained in heterogeneous conditions make it impossible to calculate the stoichiometric composition of chitosan copper complexes. Articles based on the Proceedings of the All-Russian Scientific and Technical Conference on Current Technologies and Equipment in the Textile Industry (Moscow State Textile University, November, 2007) __________ Translated from Khimicheskie Volokna, No. 2, pp. 17–9, March–April, 2008.     

Garlic's ability to prevent <Emphasis Type="Italic">in vitro</Emphasis> Cu<Superscript>2+</Superscript>-induced lipoprotein oxidation in human serum is preserved in heated garlic: effect unrelated to Cu<Superscript>2+</Superscript>-chelation

Background  

It has been shown that several extracts and compounds derived from garlic are able to inhibit Cu²⁺-induced low density lipoprotein oxidation. In this work we explored if the ability of aqueous garlic extract to prevent in vitro Cu²⁺-induced lipoprotein oxidation in human serum is affected by heating (a) aqueous garlic extracts or (b) garlic cloves. In the first case, aqueous extract of raw garlic and garlic powder were studied. In the second case, aqueous extract of boiled garlic cloves, microwave-treated garlic cloves, and pickled garlic were studied. It was also studied if the above mentioned preparations were able to chelate Cu²⁺.     

Comparison of succinylation methods for bacterial cellulose and adsorption capacities of bacterial cellulose derivatives for Cu<Superscript>2+</Superscript> ion

Bacterial cellulose (BC) was homogenously modified with succinic anhydride in N,N-dimethylacetamide/LiCl in the presence of triethylamine and heterogeneously in pyridine in the presence of 4-dimethylaminopyridine. FTIR, XRD, 13C CP MAS NMR, SEM were used to characterize BC and succinylated bacterial cellulose (SBC). For homogeneous modification, the degree of substitution (DS) of SBC differs from 0.21 to 1.45 with the variation of the adding amount of succinic anhydrate, temperature, reaction time, and the amount of triethylamine. DS and XRD profiles reveal that heterogenous reaction mainly happens on the surface of BC membrane. The adsorption capacity and mechanism of Cu²⁺ onto BC and SBC were investigated. The result shows the adsorption is affected by the morphology and the DS of adsorbents.     

Theoretical studies of local structures and spin hamiltonian parameters for Cu<Superscript>2+</Superscript> in alkali barium borate glasses

The local structures and spin Hamiltonian parameters are theoretically studied for Cu²⁺ in alkali barium borate glasses 20A₂O ? 24.5BaO · 55B₂O₃ · 0.5CuO, where A = Li, Na and K by the quantitative calculations of these parameters for tetragonally elongated octahedral 3d ⁹ clusters. The [CuO₆]^10? clusters are subject to the local relative tetragonal elongation ratios 7.8, 8.1 and 8.4% in Li, Na and K barium borate glasses, respectively, owing to the Jahn–Teller effect. The increasing (Li < Na < K) local relative elongation ratio and decreasing cubic field parameter and covalency factor are discussed in a consistent way.     

Fractionation of Soybean Globulins Using Ca<Superscript>2+</Superscript> and Mg<Superscript>2+</Superscript>: A Comparative Analysis

The substitution of CaCl₂ by MgCl₂ was undertaken in Deak’s two-step process of separating the soybean 11S and 7S globulins, aiming at higher purities and lower phytic acid (PA) contents of recovered protein fractions. The effects of pH and the addition of NaCl were also evaluated. Compared with CaCl₂, MgCl₂ reduced the PA content of the 11S-rich fraction by 63–71% but increased that of the 7S-rich fraction by 14–28%, depending on pH. Correspondingly, more Ca²⁺ was recovered in the 11S-rich fraction, while more Mg²⁺ co-precipitated with the 7S-rich fraction. NaCl increased the purity of the 11S-rich fraction and reduced its PA content, but the purity of the 7S-rich fraction was reduced by using 50–100 mM NaCl. Lowering pHs from 6.4 and 4.8 to 5.6 and 4.0 in the two precipitation steps increased the yield of both fractions. The optimized fractionating procedure was as follows: the 11S-rich fraction was precipitated at pH 5.8 by using 5 mM MgCl_2, 10 mM NaHSO₃ and 20 mM NaCl, followed by the precipitation of the 7S-rich fraction at pH 4.5. The new method provided both fractions with satisfactory protein yields (22% for 11S and 16% for 7S), purities (88% for 11S and 80% for 7S) and PA contents (0.356% for 11S and 0.882% for 7S).     

The Preparation of Phosphazene Crosslinked Cyclen Microspheres as Host for Cu<Superscript>2+</Superscript> Ions and Their Utilization as a Support Material for the Preparation of a Copper Nanocatalyst

In this study firstly, phosphazene crosslinked cyclen microspheres were synthesized. Then, supported copper nanoparticles were prepared on these phosphazene crosslinked cyclen microspheres for use as a metal catalyst. The prepared microparticles and microparticle-supported metal catalyst were characterized using FT-IR, SEM-EDX, TEM and XPS analysis. Also, the prepared metal composite was used as a catalyst for the reduction reaction of 4-nitrophenol in the presence of NaBH₄ in aqueous media. The catalytic activity of the Cu-cyclen composite catalyst was investigated using UV–Vis spectroscopy. The reduction studies were completed at four different temperatures (30–60?°C). The activation parameters were calculated from the obtained rate constants at the four different temperatures (30–60?°C). The activation energy, activation enthalpy and activation entropy for the reduction reaction of 4-NP in the presence of Cu-cyclen composite catalyst were calculated as 39.88, 36.56 and ?143.30 kJmol^?1, respectively. The total turnover frequency (TOF) for Cu-cyclen composite catalyst was 0.794 mol 4-NP (mol Cu)^?1 (min)^?1.     

Effect of Ni<Superscript>2+</Superscript>, V<Superscript>4+</Superscript> and Mo<Superscript>6+</Superscript> concentration on iron oxidation by <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis>

The ferrous oxidation ability of Acidithiobacillus ferrooxidans was studied in the presence of Ni²⁺, V⁴⁺ and Mo⁶⁺ in 9 K media in order to implement the culture in the bioleaching of spent catalyst. The rate of iron oxidation decreased with increasing concentration of metal ions, but the rate of inhibition was metal-ion dependent. The tolerance limit was critical at a concentration of 25 g/L Ni²⁺, 5 g/L V⁴⁺ and 0.03 g/L Mo⁶⁺. The growth rate of microorganisms was negligible at concentrations of 6 g/L V⁴⁺ and 0.04 g/L Mo⁶⁺. Levels and degree of toxicity of these ions have been quantified in terms of a toxicity index (TI). The toxicity order of metal ions was found to be Mo⁶⁺>V⁴⁺>Ni²⁺. The significance and relevance of multi-metal ion tolerance in Acidithiobacillus ferrooxidans has been highlighted with respect to bioleaching of spent refinery catalyst.     

Field-assisted diffusion of K<Superscript>+</Superscript>, Rb<Superscript>+</Superscript>, Cs<Superscript>+</Superscript>, Ag<Superscript>+</Superscript>, and Tl<Superscript>+</Superscript> ions in sodium silicate glass

The composition of the diffusion zone formed during the interaction between 20Na₂O · 80SiO₂ glass and molten silver, rubidium, cesium, and thallium nitrates with and without imposition of a constant electric field was determined using X-ray microanalysis. The interdiffusion coefficients and values of electrical mobility were calculated, and the parameters of temperature dependence were determined. The electrical mobility was almost independent of the size and chemical nature of a cation and was determined by the mobility of the cation included into the initial glass.     

EPR and optical studies on binary mixed alkali-alkaline earth oxide borate glasses doped with Cu<Superscript>2+</Superscript> ions

Mixed alkali alkaline earth oxide borate glasses of the composition (25 – x)Li₂O–xK₂O–12.5BaO–12.5MgO–49B₂O₃–1CuO (x = 0, 5, 10, 15 and 20 mol %) were prepared by the melt quenching technique. The X-ray diffractograms of all the glass samples were recorded at room temperature. Peak free X-ray spectra revealed the amorphous nature of all the prepared glasses. Modulated differential scanning calorimetry (MDSC) was used to determine the glass-transition temperature (T _g ). The probable mixed alkali effect was investigated using experimental techniques like density, molar volume, MDSC, electron paramagnetic resonance (EPR), and optical absorption studies. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that the ground state of \(C{u^{2 + }}is{\kern 1pt} {d_{{x^2} - {y^2}}}\) orbital (²B_1g) and the site symmetry around Cu² is tetragonally distorted octahedral. The variation of g _|| and A _|| as a function of Li₂O content was found to be nonlinear. A broad optical absorption band was observed in all the glasses containing Cu² ions corresponding to ²B_1g → ²B_2g transition. From the optical absorption studies the values of the optical band gap (E _opt) for indirect, direct transitions and Urbarch energy (ΔE) have been evaluated. By co-relating the EPR and optical absorption data, bonding parameters α², β² and β ₁ ² were evaluated.     

Synthesis and structural refinement of fully dehydrated fully Zn<Superscript>2+</Superscript>-exchanged zeolite Y (FAU), |Zn<Subscript>35.5</Subscript>|[Si<Subscript>121</Subscript>Al<Subscript>71</Subscript>O<Subscript>384</Subscript>]-FAU

The single-crystal structure of |Zn_35.5|[Si₁₂₁Al₇₁O₃₈₄]-FAU per unit cell, a = 24.794(1), dehydrated at 673 K and 1 × 10^?6 Torr, has been determined by single-crystal X-ray diffraction techniques in the space group \( Fd\bar{3}m \) at 294(1) K. The structure was refined using all intensities to the final error indices (using the 930 reflections for which F _o > 4σ(F _o)) R ₁ = 0.0448 (based on F) and wR ₂ = 0.1545 (based on F ²). About 35.5 Zn²⁺ ions per unit cell are found at an unusually large number of crystallographic distinct positions, six. The 0.5 Zn²⁺ ion per unit cell is located at the center of double 6-ring (D6R, site I; Zn(I)-O(3) = 2.642(3) Å and O(3)-Zn(I)-O(3) = 81.23(12) and 98.77(12)°). Two different site-I′ positions (in the sodalite cavities opposite D6Rs) are occupied by 14 and 3 Zn²⁺ ions per unit cell, respectively; these Zn²⁺ ions are recessed 0.67 Å and 1.02 Å, respectively, into the sodalite cavities from their 3-oxygens plane (Zn(I′a)-O(3) = 2.094(3) Å, Zn(I′b)-O(3) = 2.23(5) Å, O(3)-Zn(I′a)-O(3) = 110.32(12)°, and O(3)-Zn(I′b)-O(3) = 100.9(30)°). Site-II′ positions (in the sodalite cavities opposite S6Rs) are occupied by 6 Zn²⁺ ions, each of which extends 0.63 Å into the sodalite cavities from their 3-oxygens plane (Zn(II′)-O(2) = 2.164(3) Å and O(2)-Zn(II′)-O(2) = 112.00(12)°). Twelve Zn²⁺ ions are found at two nonequivalent sites II (in the supercage) with occupancies of 7 and 5 ions, respectively; these Zn²⁺ ions are recessed 0.52 Å and 0.96 Å, respectively, into the supercage from their 3-oxygens plane (Zn(IIa)-O(2) = 2.138(12) Å, Zn(IIb)-O(2) = 2.28(4) Å, O(2)-Zn(IIa)-O(2) = 114.2(10)°, and O(2)-Zn(IIb)-O(2) = 103.7(25)°).     

Visible up-conversion luminescence of CaWO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>,Yb<Superscript>3+</Superscript> and emission enhancement by tri-doping of Li<Superscript>+</Superscript> ions

Er³⁺,Yb³⁺ co-doped CaWO₄ polycrystalline powders were prepared by a solid-state reaction and their up-conversion (UC) luminescence properties were investigated in detail. Under 980 nm laser excitation, CaWO₄: Er³⁺,Yb³⁺ powder exhibited green UC emission peaks at 530 and 550 nm, which were due to the transitions of Er³⁺ (²H_11/2)→Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2)→Er³⁺ (⁴I_15/2), respectively. Effects of Li+ tri-doping into CaWO₄: Er³⁺,Yb³⁺ were investigated. The introduction of Li⁺ ions reduced the optimum calcinations temperature about 100 °C by a liquid-phase sintering process and the UC emission intensity was remarkably enhanced by Li⁺ ions, which could be attributed to the lowering of the symmetry of the crystal field around Er³⁺ ions.     

Structural and Activity Investigation into Al<Superscript>3+</Superscript>, La<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> Addition to the Phosphomolybdate Heteropolyanion for Isobutane Selective Oxidation

Abstract  

Twelve phosphomolybdate compounds were synthesized via cationic exchange and were of the form: M _x H_3–3x [PMo₁₂O₄₀] (M = Al, La or Ce; 0 ≤ x ≤ 1). These compounds were analyzed by XRD and adsorption isotherm. Aluminum addition causes a primitive cubic phase, while lanthanum and cerium yield body-centered structures. La and Ce addition reduces surface area of phosphomolybdate structure. Temperature-programmed experiments for the selective oxidation of isobutane yielded methacrolein, 3-methyl-2-oxetanone (lactone), acetic acid (not with aluminous compounds), propene (only with aluminous compounds), carbon dioxide and water. The preference for propene rather than acetic acid formation with Al³⁺ may be due to the smaller cation size, or primitive cubic structure. These products form via two distinct reaction processes, labeled categories 1 and 2. Category 1 formation is associated with isobutane forming products on the surface, but reaction rate determined by bulk migration of charged particles. Category 2 formation is concerned with isobutane penetrating deep within the bulk of the substrate and forming products which subsequently desorb in a series of bell-shaped humps. Methacrolein forms via both category 1 and 2, whilst all other products form via category 2 exclusively. Kinetic analysis showed apparent activation barriers for category 1 methacrolein formation range from 67 ± 2 kJ mol⁻¹ to >350 kJ mol⁻¹, and occur in groups with small, medium and large activation barriers. The addition of +3 metal cations to the phosphomolybdate anion increase thermal stability, significantly decreasing deactivation; IR spectroscopy shows that the Keggin structure remains intact during temperature-programmed experiments with the Al, La and Ce salts.     

<Superscript>22</Superscript>Na diffusion and electrical conductivity of alkali-free silicate glasses

The diffusion of sodium ions in silica glasses produced by different methods and glasses in the Al₂O₃-R₂O₃-SiO₂ (R = La, Pr, Nd, Sm, Tb) systems has been investigated by the radioactive tracer method. The diffusion mobility of ²²Na ions in the aluminosilicate glasses containing rare-earth element oxides is close to that in the KSG silica glass prepared by high-temperature hydrolysis of silicon tetrachloride SiCl₄. A comparison of the diffusion coefficients with the electrical conductivity of the glasses has demonstrated that the conduction in the KI silica glass is due to the migration of sodium ions. In the KSG glass, as well as in the aluminosilicate glasses containing rare-earth element oxides, sodium ions are not charge carriers.     

Efficient manganese luminescence induced by Ce<Superscript>3+</Superscript>-Mn<Superscript>2+</Superscript> energy transfer in rare earth fluoride and phosphate nanocrystals

Manganese materials with attractive optical properties have been proposed for applications in such areas as photonics, light-emitting diodes, and bioimaging. In this paper, we have demonstrated multicolor Mn²⁺ luminescence in the visible region by controlling Ce³⁺-Mn²⁺ energy transfer in rare earth nanocrystals [NCs]. CeF₃ and CePO₄ NCs doped with Mn²⁺ have been prepared and can be well dispersed in aqueous solutions. Under ultraviolet light excitation, both the CeF₃:Mn and CePO₄:Mn NCs exhibit Mn²⁺ luminescence, yet their output colors are green and orange, respectively. By optimizing Mn²⁺ doping concentrations, Mn²⁺ luminescence quantum efficiency and Ce³⁺-Mn²⁺ energy transfer efficiency can respectively reach 14% and 60% in the CeF₃:Mn NCs.