Theoretical and practical investigations of copper ion selective electrode with polymeric membrane based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone)

A novel ion-selective poly(vinyl chloride) (PVC) membrane sensor for Cu²⁺ ions based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone) (NDHA) as a new ionophore was prepared and studied. The best performance was observed for the membrane composition, including 30:65:1:4 (wt%) = PVC:DBP:KTpClPB:NDHA. The electrode showed a good Nernstian slope of 30.0 ± 0.5 mV/decade in a wide linear range activity of 3.0 × 10⁻⁷ to 1.0 × 10⁻² mol dm⁻³ Cu(NO₃)₂ with limit of detection 2.5 × 10⁻⁷. Sensor exhibited a fast response time (t_95% < 10 s) and could be used for about 4 months in the pH range of 3.0–7.4. The proposed potentiometric sensor was found to work satisfactorily in partially non-aqueous media up to 30 (vol%) content of methanol, ethanol and acetone. Applications of this electrode for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu²⁺ ion using EDTA, were reported. In order to predict the extraction ability of NDHA for different metallic ions, the complexes [M(NDHA)] and [M(H₂O)₆] (where M = Cu²⁺, Co²⁺, Hg²⁺, Pb²⁺, Ag⁺, Mg²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, K⁺ and Al³⁺) were investigated using ab initio theoretical calculations. The metal binding capability was evaluated using the binding energy. Results of our study could be useful for prediction of the extraction power of this Schiff base and could play a guiding role in planning experiments.     

Simultaneous extraction and determination of lead, cadmium and copper in rice samples by a new pre-concentration technique: Hollow fiber solid phase microextraction combined with differential pulse anodic stripping voltammetry

In the present work, a novel solid phase microextraction (SPME) technique using a hollow fiber-supported sol–gel combined with multi-walled carbon nanotubes, coupled with differential pulse anodic stripping voltammetry (DPASV) was employed in the simultaneous extraction and determination of lead, cadmium and copper in rice. In this technique, an innovative solid sorbent containing mixture of carbon nanotube and a composite microporous compound was developed by the sol–gel method via the reaction of tetraethylorthosilicate (TEOS) with 2-amino-2-hydroxymethyl-propane-1,3-diol (TRIS). The growth process was initiated in basic condition (pH 10–11). Afterward this sol was injected into a polypropylene hollow fiber segment for in situ gelation process. The main factors influencing the pre-concentration and extraction of the metal ions; pH of the aqueous feed solution, extraction time, aqueous feed volume, agitation speed, the role of carbon nanotube reinforcement (as-grown and functionalized MWCNT) and salting effect have been examined in detail. Under the optimized conditions, linear calibration curves were established for the concentration of Cd(II), Pb(II) and Cu(II) in the range of 0.05–500, 0.05–500 and 0.01–100 ng mL⁻¹, respectively. Detection limits obtained in this way are, 0.01, 0.025 and 0.0073 ng mL⁻¹ for Cd(II), Pb(II) and Cu(II), respectively. The relative standard deviations (RSDs) were found to be less than 5% (n = 5, conc.: 1.0 ng mL⁻¹).     

Silicon-doped hydroxyapatite prepared by a thermal technique for hard tissue engineering applications

Hydroxyapatite (HA, Ca₅(PO₄)₃OH) has been extensively used for bone implantation due to its similarity to the mineral component of bone, which makes it strongly osteoconductive. However, HA has low resorbability, and it is difficult to replace by a newly regenerated bone. Si doping can enhance the resorbability of HA by modifying its crystal structure. Here, we developed a simple thermal technique for preparing Si-doped HA from silica (SiO₂) and HA precursors, both of which are inexpensive and commercially available. This method included the physical binding of SiO₂ and HA particles, followed by pressing and sintering the mixture at an elevated temperature, which enhanced the atomic diffusion of Si into HA unit cells. We also evaluated the simulated body fluid (SBF) activity of the Si-doped HA prepared by this technique and showed that it significantly had higher resorbability and mineralizing potential compared to the pure HA. Our experimental design including, the individual precipitation and resorption assays enabled us to explain the mechanism behind the improved activity of Si-doped HA in SBF. This was attributed to the formation of new phases, such as β-tricalcium phosphate (β-TCP) and calcium silicate (Ca₂SiO₄) with higher solubility than HA on the SiO₂-contating HA during the sintering stage. This can provide some guidelines for designing new calcium phosphate-based materials for hard tissue engineering applications.     

Chemical vapor deposition of poly(3‐alkylthiophene) nanoparticles on fabric: Chemical and electrochemical characterization

Chemical vapor deposition of poly(3‐methylthiophene) and poly (3‐hexylthiophene) as conductive polymers on the surface of polyester fabrics was successfully obtained. Fourier transform infrared spectroscopy confirmed the formation of polymers on surface of fabrics (the fingerprint of polythiophenes, υ 600–1500 cm^?1). The uniformity of deposition and nanoparticles (average size of 60 nm) were proved with scanning electron microscopy. Electrochemical impedance spectroscopy showed that P3HT‐coated samples offer higher conductivity in compared to P3MT‐coated samples. The impedance modulus of P3HT‐coated samples was lowered nine times to that of row materials and reached to c8000 Ω. The samples have also shown electrochromic properties under electrical current, changing its color from yellowish green at 0 V to dark green at +12 V for poly (3‐hexylthiophene) samples and from brown at 0 V to red at +12 V for poly(3‐methylthiophene)‐coated fabrics (V = 0 V, λ = 450 nm; V = 12 V, λ = 650 nm). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40673.     

Schiff base complex of Cu immobilized on MCM-41 as reusable catalyst for efficient oxidative coupling of thiols and oxidation of sulfides using hydrogen peroxide

Schiff base complex of copper-functionalized MCM-41 (Cu-complex@MCM-41) was synthesized and used as an efficient and novel heterogeneous catalyst for the oxidative coupling of thiols into corresponding disulfides and oxidation of sulfides to sulfoxides using hydrogen peroxide (H₂O₂) as the oxidant. An aliphatic and aromatic series of sulfides and thiols including various functional groups were successfully converted into corresponding products. The all products were obtained in good to excellent yields. The mesoporous catalyst is characterized by FT-IR spectroscopy, BET, XRD, SEM, EDS and TGA. Recovery of the catalyst is easily achieved by simple filtration and reused for several consecutive runs without significant loss of its catalytic efficiency.     

Visible Light-Induced Degradation of Methylene Blue in the Presence of Photocatalytic ZnS and CdS Nanoparticles

ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method under mild conditions. The obtained nanoparticles were characterized by XRD, TEM and EDX. The results indicated that high purity of nanosized ZnS and CdS was successfully obtained with cubic and hexagonal crystalline structures, respectively. The band gap energies of ZnS and CdS nanoparticles were estimated using UV-visible absorption spectra to be about 4.22 and 2.64 eV, respectively. Photocatalytic degradation of methylene blue was carried out using physical mixtures of ZnS and CdS nanoparticles under a 500-W halogen lamp of visible light irradiation. The residual concentration of methylene blue solution was monitored using UV-visible absorption spectrometry. From the study of the variation in composition of ZnS:CdS, a composition of 1:4 (by weight) was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency of the photocatalyst nanoparticles after 6 h irradiation time was about 73% with a reaction rate of 3.61 × 10⁻³ min⁻¹. Higher degradation efficiency and reaction rate were achieved by increasing the amount of photocatalyst and initial pH of the solution.     

Enhanced shape memory effect of poly(L-lactide-co-ε-caprolactone) biodegradable copolymer reinforced with functionalized MWCNTs

Data from comprehensive thermomechanical tests of poly(L-lactide-co-ε-caprolactone) biodegradable shape memory polymer (SMP) reinforced with pristine and functionalized multiwalled carbon nanotubes (MWCNTs) are reported. The SMP specimens tested up to 500% strain and between 25 °C and 70 °C temperatures. The incorporation of functionalized MWCNTs leads to the best overall reinforcing effect in tensile modulus, yield stress, tensile strength and elongation at failure. Thermo mechanical experiments resulted that the functionalized MWCNTs increased the glass transition range of composites and changed the melting point of composites slightly. The crystallinity of composites was increased with increment of MWCNTs in composites. The shape fixity and shape recovery of composites increased slightly, while the recovery stress increased 46%. It is found that the functionalized MWCNTs prepare an effective physical cross linking and switching segments in polymer composites.     

Pure Hydrogen and Propylene Coproduction in Catalytic Membrane Reactor-Assisted Propane Dehydrogenation

Propane dehydrogenation on a commercial Pt-Sn/Al₂O₃ catalyst in a Pd-Ag membrane reactor is considered. A mathematical model is developed to evaluate the performance of the catalytic membrane reactor for the process of propane dehydrogenation. Design and operating conditions are systematically evaluated for key performance metrics such as propane conversion, propylene selectivity, hydrogen selectivity, and hydrogen recovery under different operating conditions. The results confirm that the high performance of the membrane reactor is related to the continuous removal of hydrogen from the reaction zone to shift the reaction equilibrium towards the formation of more propylene and hydrogen.     

Ni-Rhodanine Complex Supported on FSM-16 as Mesoporous Silica Support: Synthesis,Characterization and Application in Synthesis of Tri and Tetrasubstituted Imidazoles and 3,4-Dihydropyrimidine-2-(1H)-Ones

A new, efficient and recoverable heterogeneous catalyst was successfully synthesized by functionalization of mesoporous silica FSM-16. The FSM-16/CPTMS-Rh-     

Polyacrylonitrile/α-Fe2O3 Hybrid Photocatalytic Composite Adsorbents for Enhanced Dye Removal

The potential of a novel α-Fe₂O₃/polyacrylonitrile (PAN) hybrid composite adsorbent to eliminate methylene blue (MB) from aqueous solution was evaluated. PAN was selected as the base composite. The presence of α-Fe₂O₃ as nanophotocatalyst on the surface of PAN introduced an efficient photocatalytic hybrid composite adsorbent for degrading MB. Effects of α-Fe₂O₃ nanopowder loading, pH, temperature, MB initial concentration, solar light, and contact time were investigated. Langmuir, Freundlich, and Temkin isotherms were applied to analyze the adsorption behavior. The Freundlich equation provided the best correlation with experimental data. Pseudo-first-order, pseudo-second-order, and intraparticle models were employed. Thermodynamic studies indicated an endotherm and spontaneous adsorption process in a defined temperature range.