Synthesis,metal ion complexation and first use of a thia-aza substituted macrocyclic diamide as a novel sensing material for preparation of selective and sensitive poly(vinyl chloride)-membrane potentiometric sensors for Ag+ ion

A novel thia-aza substituted macrocyclic diamide 7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione (L) was synthesized and stability of its complexes with several alkaline earth, transition and heavy metal ions were studied conductometrically in methanol solution. The resulting 1:1 Ag⁺–L complex found to be the most stable one among all cation complexes studied. The optimized structures of the ligand and its Ag⁺ complex were also investigated. Based on the preliminary results thus obtained, L was used as an excellent sensing material to prepare polymeric membrane (PME) and coated graphite (CGE) silver-selective electrodes. The electrodes revealed a Nernstian behavior over wide Ag⁺ ion concentration ranges (i.e., 2.0 × 10^?6–1.0 × 10^?2 M for PME and 5.0 × 10^?7–1.0 × 10^?2 M for CGE). The potentiometric responses were independent of pH of the test solution in the range 2.9–6.8. The electrodes possessed advantages of low resistance, relatively fast response time, long lifetimes and, especially, good selectivity relative to a wide variety of other cations. The electrodes were used, as indicator electrodes, in the potentiometric titration of silver ion and in the determination of Ag⁺ ion in waste water, photographic emulsion, radiographic and photographic films and dental amalgams.     

Expedient Catalytic Access to Knöevenagel Condensation Using Sr<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript> Nanocomposite in Room Temperature

Sr₃Al₂O₆ nanocomposite was prepared by sol gel method using aluminum isopropoxide, strontium nitrate, acetylacetone and polyethylene glycol as template, followed by calcination at 900 °C. This nanocomposite was characterized by various techniques including X-ray powder diffraction, infrared spectroscopy, elemental analysis, scanning transmission microscope and transmission electron microscope. It was found that Sr₃Al₂O₆ nanocomposite successfully catalyzes the Knöevenagel condensation of aromatic aldehydes with malononitrile in room temperature in ethanol. Expedient access to the corresponding Knöevenagel adducts in moderate to high yields within 6 min is promising. The recovered catalyst was reused for three times without significant loss of activity.     

The origin of the attraction between like charged hydrophobic and hydrophilic walls confining a near-critical binary aqueous mixture with ions

The effect of ionic solute on a near-critical binary aqueous mixture confined between charged walls with different adsorption preferences is considered within a simple density functional theory. For the near-critical system containing small amounts of ions, a Landau-type functional is derived on the basis of the assumption that the correlation, ξ, and the Debye screening length, κ(-1), are both much larger than the molecular size. The corresponding approximate Euler-Lagrange equations are solved analytically for ions insoluble in the organic solvent. A nontrivial concentration profile of the solvent is found near the charged hydrophobic wall as a result of the competition between the short-range attraction of the organic solvent and the electrostatic attraction of the hydrated ions. An excess of water may be present near the hydrophobic surface for some range of the surface charge and ξκ. As a result, the effective potential between the hydrophilic and the hydrophobic surface can be repulsive far from the critical point, then attractive and again repulsive when the critical temperature is approached, in agreement with a recent experiment (Nellen et al 2011 Soft Matter 7 5360).     

Recursive self preconditioning method based on Schur complement for Toeplitz matrices

In this paper, we propose to solve the Toeplitz linear systems T _n x?=?b by a recursive-based method. The method is based on repeatedly dividing the original problem into two subproblems that involve the solution of systems containing the Schur complement of the leading principal submatrix of the previous level. The idea is to solve the linear systems S _m y?=?d, where S _m is the Schur complement of T _2m (the principal submatrix of T _n ), by using a self preconditioned iterative methods. The preconditioners, which are the approximate inverses of S _m , are constructed based on famous Gohberg–Semencul formula. All occurring matrices are represented by proper generating vectors of their displacement rank characterization. We show that, for well conditioned problems, the proposed method is efficient and robust. For ill-conditioned problems, by using some iterative refinement method, the new method would be efficient and robust. Numerical experiments are presented to show the effectiveness of our new method.     

Synthesis of functionalized 1,2,4-triazole-3-thiones from ammonium isothiocyanate,acid chlorides,and arylhydrazines

An efficient synthesis of 1-aryl-5-aryl(alkyl)-1,2-dihydro-3H-1,2,4-triazole-3-thiones via reaction between ammonium thiocyanate, acid chlorides, and arylhydrazines is described.     

Fabrication and Properties of Polycaprolactone Composites Containing Calcium Phosphate-Based Ceramics and Bioactive Glasses in Bone Tissue Engineering: A Review

Polycaprolactone (PCL) is a bioresorbable and biocompatible polymer that has been widely used in long-term implants and controlled drug release applications. However, when it comes to tissue engineering, PCL suffers from some shortcomings such as slow degradation rate, poor mechanical properties, and low cell adhesion. The incorporation of calcium phosphate-based ceramics and bioactive glasses into PCL has yielded a class of hybrid biomaterials with remarkably improved mechanical properties, controllable degradation rates, and enhanced bioactivity that are suitable for bone tissue engineering. This review presents a comprehensive study on recent advances in the fabrication and properties of PCL-based composite scaffolds containing calcium phosphate-based ceramics and bioglasses in terms of porosity, degradation rate, mechanical properties, in vitro and in vivo biocompatibility and bioactivity for bone regeneration applications. The fabrication routes range from traditional methods such as solvent casting and particulate leaching to novel approaches including solid free-form techniques.     

The stable ATA-orthogonal s-step Orthomin(k) algorithm with the CADNA library

The major drawback of the s-step iterative methods for nonsymmetric linear systems of equations is that, in the floating-point arithmetic, a quick loss of orthogonality of s-dimensional direction subspaces can occur, and consequently slow convergence and instability in the algorithm may be observed as s gets larger than 5. In [18], Swanson and Chronopoulos have demonstrated that the value of s in the s-step Orthomin(k) algorithm can be increased beyond s=5 by orthogonalizing the s direction vectors in each iteration, and have shown that the A^TA-orthogonal s-step Orthomin(k) is stable for large values of s (up to s=16). The subject of this paper is to show how by using the CADNA library, it is possible to determine a good value of s for A^TA-orthogonal s-step Orthomin(k), and during the run of its code to detect the numerical instabilities and to stop the process correctly, and to restart the A^TA-orthogonal s-step Orthomin(k) in order to improve the computed solution. Numerical examples are used to show the good numerical properties. This revised version was published online in June 2006 with corrections to the Cover Date.     

A new Cu Schiff base complex with histidine and glutaraldehyde immobilized on modified iron oxide nanoparticles as a recyclable catalyst for the oxidative homocoupling of terminal alkynes

The novel functionalized Fe₃O₄@SiO₂@APTMS@Glu-His@Cu complex was prepared from modification of iron oxide nanomagnet particles with (3-aminopropyl) trimethoxysilane (APTMS) and glutaraldehyde–histidine Schiff base followed by complexation with Cu(I) salt. Characterization of this complex was carried out by means of FTIR, XRD, SEM, TEM and VSM techniques. The complex was found to successfully catalyze the oxidative homocoupling of phenylacetylene, 4-tert-butylphenylacetylene, 1-ethynyl-4-fluorobenzene and pent-1-yn-3-ol with 67–100 % conversions and 95–100 % selectivities. Magnetic recovery and recycling of the catalyst without significant decrease in activity is described in this presentation.     

Liquid-liquid-liquid microextraction followed by HPLC with UV detection for quantitation of ephedrine in urine

Liquid-liquid-liquid microextraction (LLLME) in combination with HPLC and UV detection has been used as a sensitive method for the determination of ephedrine in urine samples. Extraction process was performed in a homemade total glass vial without using a Teflon ring, usually employed. Ephedrine was first extracted from 3.5 mL of urine sample (pH 12) into a microfilm of toluene/benzene (50:50). The analyte was subsequently back extracted into an acidic microdrop solution (pH 2) suspended in the organic phase. The extract was then injected into the HPLC system directly. An enrichment factor of 137 along with a good sample clean-up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 0.01-50 mg/L with regression coefficient corresponding to 0.998. The LODs and LOQs, based on a S/N of 3 and 10, were 5 and 10 microg/L, respectively. The method was eventually applied for the determination of ephedrine in urine sample after oral administration of 5 mg single dose of drug.