Investigations for Modification of Polyacrylamide-Bentonite by Phytic Acid and its Usability in Fe3+, Zn2+ and UO2 2+ Adsorption

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe³⁺, Zn²⁺, UO₂ ²⁺ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO₂ ²⁺ > Fe³⁺ > Zn²⁺ for PAA-B and Zn²⁺ > Fe³⁺ > UO₂ ²⁺ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO₂ ²⁺ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO₂ ²⁺ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption.     

A Ready‐to‐Use Electrochemical Kit Design for the Diagnosis of Single Nucleotide Polymorphisms

In this study, for the first time a model electrochemical kit was constructed for the detection of a functional polymorphism in catechol‐O‐methyl transferase (COMT) gene which is important for diagnosis of neuropsychiatric disorders as Alzheimer disease. The disposable pencil graphite electrode (PGE) is designed as a “kit” and the probe DNA covered PGE can detect single nucleotide polymorphisms (SNPs) from real samples based on the guanine oxidation signal even after 5 months of kit preparation (150 days durability).The detection limit (S/N=3) of the biosensor was calculated as 1.18 pmol of synthetic target sequence and 6.09×10⁵ molecules of real samples in 30 min detection time.     

A Pencil Graphite Electrode In Situ Modified by Monovalent Copper: a Promising Tool for the Determination of Methylxanthines

A pencil graphite electrode (PeGE) exhibits a promising tool for the electrochemical analysis of xanthine (Xan) and its N‐methyl derivatives (1‐, 3‐, 7‐ and 9‐mXan). The changes in their level in blood, serum, urine, as products of purine catabolism, can indicate the development of some diseases. Sensitivity‐enhanced voltammetric detection of mXans was achieved by forming of complex with Cu(I) and application of elimination procedure. The Cu(I)‐mXan complex was identified by means of titration of electrochemically produced cuprous ions by mXan. Our approach enables separation of overlapped mXan oxidation signals. Based on the obtained results, we found that the effect of methyl group position on the xanthine skeleton was significant and it was also discussed.     

The distribution of the domination number of class cover catch digraphs for non-uniform one-dimensional data

For two or more classes of points in R^d with d≥1, the class cover catch digraphs (CCCDs) can be constructed using the relative positions of the points from one class with respect to the points from one or all of the other classes. The CCCDs were introduced by Priebe et al. [C.E. Priebe, J.G. DeVinney, D.J. Marchette, On the distribution of the domination number of random class catch cover digraphs. Statistics and Probability Letters 55 (2001) 239-246] who investigated the case of two classes, X and Y. They calculated the exact (i.e., finite sample) distribution of the domination number of the CCCDs based on X points relative to Y points both of which were uniformly distributed on a bounded interval. We investigate the distribution of the domination number of the CCCDs based on data from non-uniform X points on an interval with end points from Y. Then we extend these calculations for multiple Y points on bounded intervals.     

Preparation and thermal characterization of poly(2‐vinylpyridine) copolymers coordinated to Cr nanoparticles

In this study, polystyrene‐block‐poly(2‐vinylpyridine), PS‐b‐P2VP, polyisoprene‐block‐poly(2‐vinylpyridne), PI‐b‐P2VP and poly(methyl metacrylate)‐block‐poly(2‐vinylpyridine), PMMA‐b‐P2VP, coordinated to Cr metal were synthesized and characterized by Fourier transform infrared, transmission electron microscopy and direct pyrolysis mass spectrometry techniques. Both thermal degradation mechanism and thermal stability of P2VP blocks were affected by the coordination of Cr nanoparticles to nitrogen of pyridine rings. Thermal decomposition of P2VP blocks was started by loss of pyridine units leaving an unsaturated and/or crosslinked polymer backbone that degraded at relatively high temperatures. Incorporation of Cr metal did not noticeably influence thermal behavior of PS and PI blocks. However, increase in thermal stability of PMMA block was detected and associated with inhibition of the interactions between carbonyl groups of MMA chains with nitrogen atom of pyridine ring as a consequence of coordination to metal. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural characterisation and photoluminescence of a pyridine–diimine compound

A pyridine–diimine compound N,N′-[pyridine-2,6-diyldi(E)methylylidene]bis(4-chloroaniline) is synthesised by a Schiff base condensation of 2,6-diformylpyridine with 4-chloroaniline in methanol and characterised by spectroscopic and analytical techniques. The molecular structure of the compound is determined by the single crystal X-ray diffraction study. The compound crystallizes in the monoclinic crystal system, I2/c space group with unit cell parameters a = 7.0843(12) Å, b = 6.1909(11) Å, c = 36.262(6) Å, β = 91.576(3)°, V = 1589.8(5) ų and Z = 4. There is an intermolecular hydrogen bonding in the molecule resulting in a 1D hydrogen bonding chain and these hydrogen bonding chains are linked by Cl…HC(aromatic) interactions forming a 2D network. Crystal packing of the compound is determined by Cl…HC and π–π interactions. In the fluorescence emission spectra in CH₃CN, DMF, DMSO and EtOH, the compound shows only one emission maximum.     

Finding a representative nondominated set for multi-objective mixed integer programs

In this paper, we develop algorithms to find small representative sets of nondominated points that are well spread over the nondominated frontiers for multi-objective mixed integer programs. We evaluate the quality of representations of the sets by a Tchebycheff distance-based coverage gap measure. The first algorithm aims to substantially improve the computational efficiency of an existing algorithm that is designed to continue generating new points until the decision maker (DM) finds the generated set satisfactory. The algorithm improves the coverage gap value in each iteration by including the worst represented point into the set. The second algorithm, on the other hand, guarantees to achieve a desired coverage gap value imposed by the DM at the outset. In generating a new point, the algorithm constructs territories around the previously generated points that are inadmissible for the new point based on the desired coverage gap value. The third algorithm brings a holistic approach considering the solution space and the number of representative points that will be generated together. The algorithm first approximates the nondominated set by a hypersurface and uses it to plan the locations of the representative points. We conduct computational experiments on randomly generated instances of multi-objective knapsack, assignment, and mixed integer knapsack problems and show that the algorithms work well.     

Extension of one-dimensional proximity regions to higher dimensions

Proximity regions (and maps) are defined based on the relative allocation of points from two or more classes in an area of interest and are used to construct random graphs called proximity catch digraphs (PCDs) which have applications in various fields. The simplest of such maps is the spherical proximity map which gave rise to class cover catch digraph (CCCD) and was applied to pattern classification. In this article, we note some appealing properties of the spherical proximity map in compact intervals on the real line, thereby introduce the mechanism and guidelines for defining new proximity maps in higher dimensions. For non-spherical PCDs, Delaunay tessellation (triangulation in the real plane) is used to partition the region of interest in higher dimensions. We also introduce the auxiliary tools used for the construction of the new proximity maps, as well as some related concepts that will be used in the investigation and comparison of these maps and the resulting PCDs. We provide the distribution of graph invariants, namely, domination number and relative density, of the PCDs and characterize the geometry invariance of the distribution of these graph invariants for uniform data and provide some newly defined proximity maps in higher dimensions as illustrative examples.     

Nanostructured DNA Microarrays for Dual SERS and Electrochemical Read‐out

We present a strategy to fabricate nanostructured microarrays ready to perform a dual read‐out, namely electrochemical (EC) as well as surface‐enhanced Raman spectroscopy (SERS) based detection of DNA hydridization. A polystyrene nanobeads monolayer assembly, obtained by means of a Langmuir Blodgett type technique, followed by electrochemical Au deposition, was employed to construct homogeneous nanostructures in the form of inverse‐opal nanovoids on a 32‐electrode Au microarray chip. Characterization of the obtained nanostructured electrodes of the array by means of cyclic voltammetry demonstrated high reproducibility of the surface modification process. The performance of the obtained array platform was investigated by modifying the microarray electrodes with three different oligonucleotide capture probes using a previously developed potential‐assisted surface modification protocol. Two ferrocene‐labeled target DNA sequences and one target RNA sequence with a Texas red label were detected electrochemically and via SERS, respectively.     

Crystallization kinetics of the borax decahydrate

The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, k_r and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters (K_g, k_r and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol⁻¹, respectively.