New Quenching Procedure for Preservation of Initial Polymer/Catalyst Particle Morphology in Ziegler–Natta Olefin Polymerization

Preservation of initial polymer/catalyst particle morphology under air, was examined using stopped‐flow Ziegler–Natta polymerization with various quenching conditions and post‐chemical treatments. The exposure of the initial particles to air caused the fast formation of cracks on the surface, finally leading to significant reformation of the particle shape, when polymerizing particles were washed with heptane at ?65 °C under N₂ or under CO₂. On the other hand, when the particles were washed with heptane containing an appropriate amount of tetrahydrofuran under CO₂, the particle morphology under air was almost completely maintained even after 1 h exposure. The present results are useful for various ex situ characterizations of unstable initial polymer/catalyst particles.

     

Exponential stabilization for a class of hybrid systems with mixed delays in state and control

This paper proposes a switching design for the exponential stabilization problem of hybrid systems with mixed time-delays in both the state and control. By using an improved Lyapunov–Krasovskii functional, a memoryless switching controller for the exponential stabilization of the system is designed in terms of linear matrix inequalities. The approach also allows us to compute simultaneously the two bounds that characterize the exponential stability rate of the solution.     

Two- and three-dimensional networks of gadolinium(III) with dicarboxylate ligands: synthesis, crystal structure, and magnetic properties

Four gadolinium(III) complexes with dicarboxylate ligands of formulas [Gd2(mal)3(H2O)5]n.2nH2O (1), [Gd2(mal)3(H2O)6]n (2), [NaGd(mal)(ox)(H2O)3]n (3), and [Gd2(ox)3(H2O)6]n.2.5nH2O (4) (mal = malonate; ox = oxalate) have been prepared, and their magnetic properties have been investigated as a function of the temperature. The structures of 1-3 have been determined by X-ray diffraction methods. The crystal structure of 4 was already known, and it is made of hexagonal layers of Gd atoms that are bridged by bis-bidentate oxalate. Compound 1 is isostructural with the europium(III) malonate complex [Eu2(mal)3(H2O)5]n.2nH2O,1 whose structure was reported elsewhere. The Gd atoms in 1 define a two-dimensional network where a terminal bidentate and bridging bidentate/bis-monodentate and tris-bidentate coordination modes of malonate occur. Compound 2 has a three-dimensional structure with a structural phase transition at 226 K, which involves a change of the space group from I2/a to Ia. Although its structure at room temperature was already known, that below 226 K was not. Pairs of Gd atoms with a double oxo-carboxylate bridge occur in both phases, and the main differences between both structures deal with the Gd environment and the H-bond pattern. 3 is also a three-dimensional compound, and it was obtained by reacting Gd(III) ions with malonic acid in a silica gel medium. Oxalic acid results as an oxidized product of the malonic acid, and single crystals of the heteroleptic complex were produced. The Gd atoms in 3 are connected through bis-bidentate oxalate and carboxylate-malonate bridges in the anti-anti and anti-syn coordination modes. Compounds 1 and 2 exhibit weak but significant ferromagnetic couplings between the Gd(III) ions through the single (1) and double (2) oxo-carboxylate bridges, whereas antiferromagnetic interactions across the bis-bidentate oxalate account for the overall antiferromagnetic behavior observed in 3 and 4.     

UV Index on tilted surfaces

Solar ultraviolet erythemal irradiance (UVER) has been studied on inclined planes with different orientations in Valencia, Spain. To do this a platform was designed that could turn through 90 degrees on its own axis. The radiometers were inclined at an angle close to the latitude of Valencia (39.5 degrees N). Using two timers the platform could be turned through 90 degrees every 5 min. On clear or partially cloudy days, including those with different turbidity values, it was observed that the UVER showed a maximum at 1200 h GMT, very close to solar noon, in the north and south positions, while the maximum for east and west orientations was found at approximately one hour before and one hour after midday respectively. It was also observed how the irradiance for the south orientation was greater and for the north was less than for the horizontal plane, as well as the opposite performances of the east and west orientations, for four days close to the summer and winter solstices and each equinox. Some experimental results were also compared with the results from the SMARTS2.9 model for the same conditions. It was found that the model frequently overestimated the experimental data. With respect to the maximum calculated UV Index in the different planes this was always higher for the south orientation than for the north, while it was similar for east and west orientations throughout the year. Finally the accumulated erythemal dosage for the considered period was obtained as a function of phototype and orientation, confirming that the accumulated erythemal dosage decreased by around 37% in the north orientation compared to the horizontal value, while in the south position it was only 6% less and some 20% and 15% less in the east and west positions, respectively.     

Material force method: theoretical and numerical aspects in nonlinear electro-elastostatics

Formulations of the spatial and material motion problem in nonlinear electroelastostatics are considered in this work by a virtual work approach. Based on these formulations, a finite element discretization is realized and a numerical example is presented to demonstrate possible uses of the material force method in studying the closing process of cracks. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Creating Very True Quantum Algorithms for Quantum Energy Based Computing

An interpretation of quantum mechanics is discussed. It is assumed that quantum is energy. An algorithm by means of the energy interpretation is discussed. An algorithm, based on the energy interpretation, for fast determining a homogeneous linear function f(x) := s.x = s ₁ x ₁ + s ₂ x ₂ + ? + s _N x _N is proposed. Here x = (x ₁, … , x _N ), x _j ∈ R and the coefficients s = (s ₁, … , s _N ), s _j ∈ N. Given the interpolation values \((f(1), f(2),...,f(N))=\vec {y}\), the unknown coefficients \(s = (s_{1}(\vec {y}),\dots , s_{N}(\vec {y}))\) of the linear function shall be determined, simultaneously. The speed of determining the values is shown to outperform the classical case by a factor of N. Our method is based on the generalized Bernstein-Vazirani algorithm to qudit systems. Next, by using M parallel quantum systems, M homogeneous linear functions are determined, simultaneously. The speed of obtaining the set of M homogeneous linear functions is shown to outperform the classical case by a factor of N × M.     

Pressure effects on the thermodynamic and mechanical properties of zinc-blende ZnTe compound

In this paper, the moment method in statistical mechanics has been employed to study the pressure effects on thermodynamic and mechanical properties of zinc-blende zinc telluride using many-body potential. We have derived the analytical expressions of the pressure-dependent lattice parameter, volume compression as well as mean-square displacement of zinc-blende type compound. Numerical calculations performed for ZnTe compound up to 12 GPa are found to be in good and reasonable agreement with available experimental data as well as with previous theoretical studies. These results have been used to evaluate the bulk modulus and its first pressure derivative of ZnTe. The present moment method has taken into account the quantum zero-point vibrations at low temperature and the higher-order anharmonic terms in the atomic displacements. This research shows the advantage of moment method on extensively studying thermo-mechanical properties of materials under high pressures.     

Rayleigh waves in an isotropic elastic half-space coated by a thin isotropic elastic layer with smooth contact

In the present paper, we are interested in the propagation of Rayleigh waves in an isotropic elastic half-space coated with a thin isotropic elastic layer. The contact between the layer and the half space is assumed to be smooth. The main purpose of the paper is to establish an approximate secular equation of the wave. By using the effective boundary condition method, an approximate, yet highly accurate secular equation of fourth-order in terms of the dimensionless thickness of the layer is derived. From the secular equation obtained, an approximate formula of third-order for the velocity of Rayleigh waves is established. The approximate secular equation and the formula for the velocity obtained in this paper are potentially useful in many practical applications.     

Low-molecular weight protein profiling of genetically modified maize using fast liquid chromatography electrospray ionization and time-of-flight mass spectrometry

In this work, the use of liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC-TOFMS) has been evaluated for the profiling of relatively low-molecular weight protein species in both genetically modified (GM) and non-GM maize. The proposed approach consisted of a straightforward sample fractionation with different water and ethanol-based buffer solutions followed by separation and detection of the protein species using liquid chromatography with a small particle size (1.8 μm) C(18) column and electrospray-time-of-flight mass spectrometry detection in the positive ionization mode. The fractionation of maize reference material containing different content of transgenic material (from 0 to 5% GM) led to five different fractions (albumins, globulins, zeins, zein-like glutelins, and glutelins), all of them containing different protein species (from 2 to 52 different species in each fraction). Some relevant differences in the quantity and types of protein species were observed in the different fractions of the reference material (with different GM contents) tested, thus revealing the potential use of the proposed approach for fast protein profiling and to detect tentative GMO markers in maize.     

Degradable conjugates from oxanorbornadiene reagents

Oxanorbornadienedicarboxylate (OND) reagents were explored for purposes of binding and releasing drugs from serum albumins as representative macromolecular carriers. Being highly reactive Michael acceptors, ONDs form adducts with thiols and amines, which then undergo retro-Diels-Alder fragmentation. A study of more than 30 model adducts revealed a number of modifications that can be used to influence adduct stability. For the most reactive OND linkers, the labeling of the single available bovine serum albumin (BSA) cysteine residue was complete within minutes at a mid-micromolar concentration of reactants. While a selectivity of greater than 1000-fold for thiol over amine was observed with model amino acids, the labeling of protein amines with ONDs is fast enough to be practical, as demonstrated by the reaction with thiol-depleted BSA. The OND-amine adducts were found to be up to 15 times more stable than OND-thiol adducts, and to be sensitive to acid by virtue of a stereochemically dependent acceleration of cycloreversion. The release rate of fluorescent cargo from serum albumins was tuned by selecting the coupling partners: the available half-lives ranged from 40 min to 7 days at 37 °C. Such versatility of release profiles from protein carriers, controlled by the nature of the OND linkage, is a useful addition to the drug delivery toolbox.