Effect of the structure of titanium–magnesium catalysts on the morphology of polyethylene produced

The structure and formation of polyethylene (PE) particles on supported titanium–magnesium catalysts having different structural characteristics (sizes of microcrystallites, mesopores, and subparticles) were studied for the first time. Scanning electron microscopy was used to identify structural elements of the polymer particles formed over such catalysts and to reveal morphological changes in the growing polymer particles when the yield was increased from approximately 0.2 g PE/g catalyst to approximately 13 kg PE/g catalyst. A relationship was found between structural characteristics of the porous catalyst particles, morphology of the nascent polymer particles, and bulk density of the polymer powder. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2298–2308     

Ligational behavior of new mononucleating NOO ethyl pyruvate Schiff base towards 3d metal(II) ions: an emphasis on antiproliferative and photocleavage property

A series of Co(II), Ni(II), Cu(II), and Zn(II) complexes of a tridentate hydrazone were prepared and characterized by various spectro‐analytical techniques and magnetic moment studies. The complexes were found to be monomeric and non‐electrolytes. The copper complex is electrochemically active in the applied potential range. The compounds synthesized in the present study have shown promising antiproliferative activity when screened using the in vitro method against two human cancer cell lines: HeLa and HepG2. The Escherichia coli DNA‐binding properties of all the compounds were investigated with UV–visible absorption spectrophotometric titrations, viscosity measurements, DNA melting experiments and gel electrophoreses measurements. The compounds were demonstrated to act as DNA intercalators with appreciable DNA‐binding constant values. Copyright © 2012 John Wiley & Sons, Ltd.     

Novel Azobenzene-Functionalized Polyelectrolytes of Different Substituted Head Groups 2: Control of Surface Wetting in Self-Assembled Multilayer Films

A novel set of light-responsive polyelectrolytes has been developed and studied, to control and tune surface wettability by introducing various types of substituted R head-groups of azo polyelectrolytes in self-assembled multilayer (SAMU) films. As part of a larger project to develop polymer surfaces where one can exert precise control over properties important to proteins and cells in contact, photo-reversibly, we describe here how one can tune quite reliably the contact angle of a biocompatible SAMU, containing a photo-reversible azo chromophore for eventual directed cell growth. The azo polyelectrolytes described here have different substituted R head-group pairs of shorter-ionized hydrophilic COOH and SO₃H, shorter non-ionized hydrophobic H and OC₂H₅, and larger non-ionized hydrophobic octyl C₈H₁₇ and C₈F₁₇, and were employed as polyanions to fabricate the SAMU onto silicon substrates by using the counter-charge polycation PDAC. The prepared SAMU films were primarily characterized by measurement of their contact angles with water. The surface wetting properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes through their degree of ionization, size, hydrophobicity/hydrophilicity, solubility, conformation, and inter-polymeric association and intra-polymeric aggregation. All these factors appeared to be inter-related, and influenced variations in hydrophobic/hydrophilic character to different extents of aggregates/non-aggregates in solution because of solvation effects of the azo polyanions, and were thus manifested when adsorbed as thin films via the SAMU deposition process. For example, one interesting observation is significantly higher contact angles of 79° for SAMU films of larger octyl R groups of PAPEA-C₈F₁₇ and PAPEA-C₈H₁₇ than for others with contact angles of 64° observed for non-polar R-groups of OC₂H₅ and H. Furthermore, lower contact angle values of 59° for SAMU films with polar R-groups of COOH and SO₃H relative to that of non-polar R-groups are in accordance with their expected order of the hydrophilicity or hydrophobicity. It is possible that the large octyl groups are more effective in shielding the ionic functional groups on the substrate surface, and contributed less to the water drop-molecule interactions with ionic groups of the PDAC and/or AA groups. In addition, higher hydrophobicity of the SAMU films may be due to the incorporation of bulky and hydrophobic groups in these polyelectrolytes, which can produce aggregates on the surfaces of the SAMU films. Through understanding and controlling the complex aggregation behavior of the different substituted R-groups of these azo polyelectrolytes, and hence their adsorption on substrates, it appears possible to finely tune the surface energy of these biocompatible films over a wide range, enhance the photo-switching capabilities of the SAMU films, and tailor other surface properties for the development and application of new devices in diverse areas of microfluidics, specialty coatings, sensors, and biomedical sciences.     

Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid‐functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols

In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3‐aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid‐substituted imidazolium‐based ionic liquid onto the surface of these particles via a multi‐component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP‐OES. The nanostructures have spherical shapes that ranged in size from 80 to 100 nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity.     

Factors affecting the strengths of σ-hole electrostatic potentials

A σ-hole is a region of diminished electronic density on the extension of a covalent bond to an atom. This region often exhibits a positive electrostatic potential, which allows attractive noncovalent interactions with negative sites. In this study, we have systematically examined the dependence of σ-hole potentials upon (a) the atom having the σ-hole, and (b) the remainder of the molecule. We demonstrate that not only relative electron-attracting powers need to be considered, but also relative charge capacities (or polarizabilities), and that other factors can also have significant roles.     

One ligand capable of in situ reaction in a mixed-ligand system with two new different frameworks

The in situ ligand 2,3-pyrazinedicarboxylic acid (2,3-H₂pzdc) mixed with 1,1′-(1,4-butanediyl)bis(benzimidazole) (bbbi) is used to form two coordination polymers ([Cd(2,3-pzdc)(bbbi)] (1) and [Cd₂Cl₃(2-pzc)(bbbi)₂] (2)) under hydrothermal conditions. Complex 1 was obtained in the absence of in situ reaction and 2 was synthesized with 2,3-H₂pzdc in situ generating 2-pyrazinecarboxylate (2-pzc^?). The structural details reveal that 1 has a 3D framework with dia topology, and 2 is a 2D layer structure and develops a 3D supramolecular structure via strong π?π stacking interactions. The ligand effects were compared for the two frameworks. In addition, fluorescence properties and thermal stabilities of 1 and 2 in the solid were studied.     

Flow of a micropolar fluid due to a porous stretching sheet and heat transfer

The present work investigates the micropolar fluid flow due to a permeable stretching sheet and the resulting heat transfer. Unlike the existing numerical works on the flow phenomenon in the literature, the prime interest here is to analytically work out shape of the solutions and identify whether they are unique. Indeed, unique solutions are detected and presented in the exact formulas for the associated boundary layer equations. Temperature field influenced by the microrotation is also mathematically resolved in the cases of constant wall temperature, constant heat flux and Newtonian heating. To discover the salient physical features of many mechanisms acting on the considered problem, it is adequate to have the analytical velocity and temperature fields and also closed-form skin friction/couple stress/heat transfer coefficients, all as given in the current paper. For instance, the practically significant rate of heat transfer is represented by a single formula valid for all three temperature cases.     

A mass‐conservative staggered immersed boundary model for solving the shallow water equations on complex geometries

In this work, an approach is proposed for solving the 3D shallow water equations with embedded boundaries that are not aligned with the underlying horizontal Cartesian grid. A hybrid cut‐cell/ghost‐cell method is used together with a direction‐splitting implicit solver: Ghost cells are used for the momentum equations in order to prescribe the correct boundary condition at the immersed boundary, while cut cells are used in the continuity equation in order to conserve mass. The resulting scheme is robust, does not suffer any time step limitation for small cut cells, and conserves fluid mass up to machine precision. Moreover, the solver displays a second‐order spatial accuracy, both globally and locally. Comparisons with analytical solutions and reference numerical solutions on curvilinear grids confirm the quality of the method. Copyright © 2015 John Wiley & Sons, Ltd.     

Exact pressure integrations on submerged bodies in waves using a quadtree adaptive mesh algorithm

The development of an adaptive free surface, mesh cutting, methodology, in order to analytically integrate pressures on varying wet parts of partially submerged surfaces in the presence of waves, is presented. Given a function of free‐surface elevation, the algorithm checks for the intersection of the body with the free surface and, based on user‐defined parameters, modifies the initial mesh, by subdividing the elements where necessary and eliminating others, via a quadtree approach. Redundant sub‐divisions, generated in the quad‐division process, are partially eliminated, but the quadrilateral nature of the elements is always kept. The free‐surface function must be single‐valued and its definition domain simply connected. Hydrostatic and Froude–Krylov forces are computed exactly on each panel by means of analytical formulations, which are derived and presented, based on the theory of linear gravity waves and from applying Green's theorem. Copyright © 2014 John Wiley & Sons, Ltd.