The double deflating technique for irreducible singular M-matrix algebraic Riccati equations in the critical case

As is known, Alternating-Directional Doubling Algorithm (ADDA) is quadratically convergent for computing the minimal nonnegative solution of an irreducible singular M-matrix algebraic Riccati equation (MARE) in the noncritical case or a nonsingular MARE, but ADDA is only linearly convergent in the critical case. The drawback can be overcome by deflating techniques for an irreducible singular MARE so that the speed of quadratic convergence is still preserved in the critical case and accelerated in the noncritical case. In this paper, we proposed an improved deflating technique to accelerate further the convergence speed – the double deflating technique for an irreducible singular MARE in the critical case. We proved that ADDA is quadratically convergent instead of linearly when it is applied to the deflated algebraic Riccati equation (ARE) obtained by a double deflating technique. We also showed that the double deflating technique is better than the deflating technique from the perspective of dimension of the deflated ARE. Numerical experiments are provided to illustrate that our double deflating technique is effective.     

Condensed Mode Cooling of Ethylene Polymerization in Fluidized Bed Reactors

This review gives an overview of the evolution of the technology of condensed mode cooling, primarily for the case of ethylene polymerization on supported catalysts in fluidized bed reactors. It is well known that this mode of heat removal is quite effective in allowing polyolefin manufacturers to increase significantly production rates. What is perhaps less well understood are all of the issues that, in addition to the effect of the latent heat of vaporization of injected liquid components, also have an impact on the rate of production and behavior of the reactor. However, the liquid components injected into the reactor can vaporize rapidly under full‐scale conditions, leaving behind several heavy components (with respect to ethylene) that have numerous effects on how the particles behave, on the reaction rate, and on fluidization, fouling, and other parameters related to reactor and process performance.     

Unveiling the Layer‐Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction

Two‐dimensional (2D) PtSe₂ shows the most prominent layer‐dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure–activity correlations in 2D systems. Here, starting with the synthesis of single‐crystalline 2D PtSe₂ with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer‐dependent HER catalytic activity of 2D PtSe₂ from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe₂ flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure–activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.     

Preparation and characterization of magnetic graphene nanocomposite containing Cu(proline)2 as catalyst for asymmetric aldol reactions

Research on Chemical Intermediates - A new catalyst has been prepared via immobilization of Cu(proline)2 complex onto the surface of magnetic graphene. The fabricated nanocatalyst was characterized...     

High-Throughput Synthesis and Characterization of Aryl Silicones by Using the Piers–Rubinsztajn Reaction

Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a “one-off” formulation and test process. Herein, it is demonstrated that high-throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then the relative impact of different aryl groups on their physical properties is assessed. Aromatic groups were incorporated into polydimethylsiloxane (PDMS) elastomers by exploiting the relative reactivity of different functional groups in the Piers–Rubinsztajn reaction. To analyze trends in the silicone mechanical properties as a function of increasing aryl concentration—structure/property relationships—libraries of elastomers were both quickly synthesized and characterized by using high-throughput suites starting from low viscosity silicone oils/monomers in 96-well plates. Liquid handling parameters were optimized to effectively work with the silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased the silicone elastomer modulus by approximately 50 % (at a crosslink density of 6 %); elastomers prepared with an aromatic crosslinker with three contact points led to much higher moduli compared with those with one contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenylsilicones.     

Pull-in Instability Analysis of Nanoelectromechanical Rectangular Plates Including the Intermolecular,Hydrostatic, and Thermal Actuations Using an Analytical Solution Methodology

The current paper presents a thorough study on the pull-in instability of nanoelectromechanical rectangular plates under intermolecular, hydrostatic, and thermal actuations. Based on the Kirchhoff theory along with Eringen's nonlocal elasticity theory, a nonclassical model is developed. Using the Galerkin method(GM), the governing equation which is a nonlinear partial differential equation(NLPDE) of the fourth order is converted to a nonlinear ordinary differential equation(NLODE) in the time domain. Then, the reduced NLODE is solved analytically by means of the homotopy analysis method. At the end, the effects of model parameters as well as the nonlocal parameter on the deflection, nonlinear frequency, and dynamic pull-in voltage are explored.     

Total Synthesis of Callyspongiolide,Part 2: The Ynoate Metathesis/cis-Reduction Strategy

The macrocyclic core of the cytotoxic marine natural product callyspongiolide ( 1 ) was forged by ring-closing alkyne metathesis (RCAM) of an ynoate precursor using a molybdenum alkylidyne complex endowed with triarylsilanolate ligands as the catalyst. This result is remarkable in view of the failed attempts documented in the literature at converting electron deficient alkynes with the aid of more classical catalysts. The subsequent Z-selective semi-reduction of the resulting cycloalkyne by hydrogenation over nickel boride required careful optimization in order to minimize overreduction and competing dehalogenation of the compound's alkenyl iodide terminus as needed for final attachment of the side chain of 1 by Sonogashira coupling. The required cyclization precursor itself was prepared via Kocienski olefination.     

Cyclometallated 1,2,3-triazol-5-ylidene iridium(III) complexes: synthesis,structure, and photoluminescence properties

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Raman Scattering in Langasite-Family Crystals

Crystallography Reports - Raman scattering spectra have been investigated in La3Ga5SiO14 langasite crystals with Cr and Fe impurities and La3Ga5.25Ta0.25Si0.5O14 crystalline solid solution. It is...     

Development of a method for quantitative determination of the cytotoxic agent piplartine (piperlongumine) in multiple skin layers

This study reports the development of a simple and reproducible method, with high rates of recovery, to extract the cytotoxic agent piplartine from skin layers, and a sensitive and rapid UV‐HPLC method for its quantification. Considering the potential of piplartine for topical treatment of skin cancer, this method may find application for formulation development and pharmacokinetics studies to assess cutaneous bioavailability. Porcine skin was employed as a model for human tissue. Piplartine was extracted from the stratum corneum (SC) and remaining viable skin layers (VS) using methanol, vortex homogenization and bath sonication, and subsequently assayed by HPLC using a C₁₈ column, and 1:1 (v/v) acetonitrile–water (adjusted to pH 4.0 with acetic acid 0.1%) as mobile phase. The quantification limit of piplartine was 0.2 μg/mL (0.6 μm ), and the assay was linear up to 5 μg/mL (15.8 μm ), with within‐day and between‐days assay coefficients of variation and relative errors <15%. Piplartine recovery from SC and VS varied from 86 to 96%. The method was suitable to assay samples from skin penetration studies, enabling detection of differences in cutaneous delivery in different skin compartments resulting from treatment with various formulations and time periods.