Tri-nuclear phthalocyanine complexes carrying N/O donor ligands as hydrogen peroxide catalysts,and their bleaching activity measurements by an online spectrophotometric method

A phthalocyanine (4) with four salicylhydrazone ligating groups that are directly linked through oxygen bridges to the macrocyclic core has been synthesized by condensation of tetrakis(4-formylphenoxy)phthalocyaninato zinc(II) (3) with salicylhydrazine. Salicylhydrazine was crystallized in methanol during the synthetic procedure. The crystal structure has triclinic space group P-1 with a = 5.8292(6) Å, b = 7.3039(7) Å, c = 17.9798(18) Å, α = 84.272(8)°, β = 89.184(8)°, γ = 81.469(8)°, and Z = 4. Intramolecular O–H?O and intermolecular O–H?O, N–H?N, N–H?O hydrogen bonds were determined in the crystal structure. In addition, there is a weak C–H?π interaction. Complexation on the periphery to yield tri-nuclear Zn(II)Pcs (5–7) was performed through the reaction of a Schiff base-substituted phthalocyanine (4) with MnCl₂·4H₂O, CoCl₂·6H₂O, or Ni(OAc)₂ salts. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–Vis, ICP-OES (inductively coupled plasma optical emission spectroscopy), mass spectroscopies, and elemental analyses were applied to characterize the prepared compounds. Bleach catalyst activity of the prepared phthalocyanine complexes (5–7) was examined by the degradation of morin and curcumin, respectively. The catalysts had better activity for color removing in solutions at ambient temperature than to that of tetraacetylethylenediamine (TAED).     

Aluminum Redistribution during the Preparation of Hierarchical Zeolites by Desilication

A literature survey reveals a prominent reduction in the concentration of Brønsted acid sites in hierarchically organized zeolites with increasing mesoporous or external surface area independent of the framework type or synthesis route; this suggests a common fundamental explanation. To determine the cause, nature, and impact of the underlying changes in aluminum speciation, this study combines a multitechnique analysis that integrates basic characterization, a detailed synchrotron XRD and multiple‐quantum NMR spectroscopy assessment, and catalytic tests to correlate evolution of the properties with performance during successive steps in the preparation of hierarchical MFI‐type zeolites by desilication. The findings, subsequently generalized to FAU‐ and BEA‐type materials, identify the crucial impact of calcination on the protonic form, which is an integral step in the synthesis and regeneration of zeolite catalysts; on aluminum coordination; and the associated acidity trends.     

Electronic transport in strained p-modulation Be-doped Ga0.8In0.2As/GaAs single quantum well

We report on the electronic transport properties of p-modulation Be-doped Ga_0.8In_0.2As/GaAs single quantum well. The experiments included the spectral photoluminescence between 8 and 300?K, and Hall effect measurements at temperatures between 14 and 300?K. The effect of strain which induces splitting of the valence band as light and heavy hole bands on transport is discussed. The calculated band alignment of the GaInAs sample using model-solid theory including strain effects indicates large conduction band discontinuities and a much smaller valance band discontinuity in GaInAs. The effect of the conduction and valance band discontinuity on the electronic transport properties is also discussed.     

Control of CO2 adsorption heats by the Al distribution in FER zeolites

Proper combination of template and optimized reaction conditions provides zeolite FER with homogeneous distribution of Al in the framework; this results in a new zeolite adsorbent exhibiting a constant heat of CO(2) adsorption.     

Photocatalyzed sulfide oxygenation with water as the unique oxygen atom source

In our research program aiming to develop new ruthenium-based polypyridine catalysts for oxidation we were interested in combining a photosensitizer and a catalytic fragment within the same complex to achieve catalytic light-driven oxidation. To respond to the lack of such conjugates, we report here a new catalytic system capable of using light to activate water molecules in order to perform selective sulfide oxygenation into sulfoxide via an oxygen atom transfer from H(2)O to the substrate with a TON of up to 197 ± 6. On the basis of electrochemical and photophysical studies, a proton-coupled electron-transfer process yielding to an oxidant Ru(IV)-oxo species was proposed. In particular, the synergistic effect between both partners in the dyad yielding a more efficient catalyst compared to the bimolecular system is highlighted.     

Primitivity of finitely presented monomial algebras

We study prime monomial algebras. Our main result is that a prime finitely presented monomial algebra is either primitive or it has GK dimension one and satisfies a polynomial identity. More generally, we show that this result holds for the class of automaton algebras; that is, monomial algebras that have a basis consisting of the set of words recognized by some finite state automaton. This proves a special case of a conjecture of the first author and Agata Smoktunowicz.     

Customer rebates and retailer incentives in the presence of competition and price discrimination

Promotions are important tools for matching supply and demand in many industries. In the United States automotive industry, promotions are frequently offered, which may be given directly to customers (rebates) or given to dealers (incentives) to stimulate demand. We analyze the performance of customer rebate and retailer incentive promotions under competition. We study a setting with two manufacturers making simultaneous pricing and promotion decisions, and with two price-discriminating retailers as Stackelberg followers making simultaneous order quantity decisions. In the benchmark case with no promotions, we characterize the equilibria in closed form. We find that retailer incentives can be used by manufacturers to simultaneously improve each of their profits but can potentially lead to lower retailer profits. When manufacturers use customer rebates, we show that a manufacturer is able to decrease the profit of her competitor while increasing her own profit, although she is also at risk for her competitor to use rebates in a similar fashion. Unlike the monopoly case where the manufacturers are always better off with retailer incentives, customer rebates can be more profitable under some cases in the presence of competition. Using numerical examples we generate insights on the manufacturers’ preference of promotions in different market settings.     

3D Plotted PCL Scaffolds for Stem Cell Based Bone Tissue Engineering

The ability to control the architecture and strength of a bone tissue engineering scaffold is critical to achieve a harmony between the scaffold and the host tissue. Rapid prototyping (RP) technique is applied to tissue engineering to satisfy this need and to create a scaffold directly from the scanned and digitized image of the defect site. Design and construction of complex structures with different shapes and sizes, at micro and macro scale, with fully interconnected pore structure and appropriate mechanical properties are possible by using RP techniques. In this study, RP was used for the production of poly(ε-caprolactone) (PCL) scaffolds. Scaffolds with four different architectures were produced by using different configurations of the fibers (basic, basic-offset, crossed and crossed-offset) within the architecture of the scaffold. The structure of the prepared scaffolds were examined by scanning electron microscopy (SEM), porosity and its distribution were analyzed by micro-computed tomography (µ-CT), stiffness and modulus values were determined by dynamic mechanical analysis (DMA). It was observed that the scaffolds had very ordered structures with mean porosities about 60%, and having storage modulus values about 1 × 10⁷ Pa. These structures were then seeded with rat bone marrow origin mesenchymal stem cells (MSCs) in order to investigate the effect of scaffold structure on the cell behavior; the proliferation and differentiation of the cells on the scaffolds were studied. It was observed that cell proliferation was higher on offset scaffolds (262000 vs 235000 for basic, 287000 vs 222000 for crossed structure) and stainings for actin filaments of the cells reveal successful attachment and spreading at the surfaces of the fibers. Alkaline phosphatase (ALP) activity results were higher for the samples with lower cell proliferation, as expected. Highest MSC differentiation was observed for crossed scaffolds indicating the influence of scaffold structure on cellular activities.     

Role of fluctuational electrodynamics in near-field radiative heat transfer

The objective of this paper is to discuss the role of fluctuational electrodynamics in the context of a generalized radiative heat transfer problem. Near-field effects, including the interference phenomenon and radiation tunneling, are important for applications to nanostructures. The classical theory of radiative transfer cannot be readily applied as the feature size approaches the dominant wavelength of radiative emission. At all length scales, however, propagation of radiative energy is properly represented by the electromagnetic wave approach, which requires the solution of the Maxwell equations. Fluctuational electrodynamics provides a model for thermal emission when solving a near-field radiation heat transfer problem, and the fluctuation-dissipation theorem provides the bridge between the strength of the fluctuations of the charges inside a body and its local temperature. This paper provides a complete and systematic derivation of the near-field radiative heat flux starting from the Maxwell equations. An illustrative example of near-field versus far-field radiation heat transfer is presented, and the length scale for transition from near- to far-field regime is discussed; the results show that this length scale can be as large as three times than predicted from Wien's law.     

Linear Huber M-Estimator Under Ellipsoidal Data Uncertainty

The purpose of this note is to present a robust counterpart of the Huber estimation problem in the sense of Ben-Tal and Nemirovski when the data elements are subject to ellipsoidal uncertainty. The robust counterparts are polynomially solvable second-order cone programs with the strong duality property. We illustrate the effectiveness of the robust counterpart approach on a numerical example.