β-Tetra-brominated meso-tetraphenylporphyrin: A conformational study and application to the Mn-porphyrin catalyzed epoxidation of olefins with tetrabutylammonium oxone

X-ray crystallographic studies have shown that the free base β-tetra-brominated meso-tetraphenylporphyrin (H₂TPPBr₄) has a slightly ruffled structure with the dihedral angles of 70.1–79.2° between the phenyl groups and the porphyrin mean plane. The N(pyrrole)–N(pyrrolenine) distance is very similar to that of the standard planar porphyrins. The decreased N–H bond length of H₂TPPBr₄ with respect to that of meso-tetraphenylporphyrin (H₂TPP) seems to be due to the weaker intramolecular hydrogen bond of the former relative to the latter caused by the electron-withdrawing effects of the β-bromine substituents. The large red shifts of the Soret and Q(0,0) bands of H₂TPPBr₄ in comparison with those of H₂TPP, in spite of the nearly planar porphyrin core of the compound, also may be explained on the basis of the electron-withdrawing effects of the bromine atoms. Oxidation of styrene, the para-substituted derivatives and cyclooctene with tetrabutylammonium oxone in the presence of catalytic amounts of β-tetra-brominated meso-tetraphenylporphyrinatomanganese(III) acetate immediately gives the epoxide as the sole product. Terminal double bonds and unconjugated ones are less reactive than the conjugated double bonds and show lower selectivities. Catalytic activity of the electron-deficient Mn(H₂TPPBr₄)OAc dramatically depends on the Co-catalytic activity of the nitrogen donors as the axial base. The best axial bases are the nitrogenous donors with mixed σ- and π-donor ability to the metal centre.     

Self-propagating assembly of a molecular-based multilayer

Accelerated growth of a molecular-based material that is an active participant in its continuing self-propagated assembly has been demonstrated. This nonlinear growth process involves diffusion of palladium into a network consisting of metal-based chromophores linked via palladium.     

LMI‐based criterion for the robust guaranteed cost control of uncertain switched neutral systems with time‐varying mixed delays and nonlinear perturbations by dynamic output feedback

This article reports on an investigation into robust guaranteed cost control (GCC) for uncertain switched neutral systems (USNSs) with interval time‐varying mixed delays and nonlinear perturbations via dynamic output feedback. Delay‐dependent sufficient conditions are suggested to guarantee the robust exponential stability and to obtain robust GCC for USNSs using the average dwell time approach and the piecewise Lyapunov function technique in terms of a set of linear matrix inequalities. The problem of uncertainty in the system model is solved by deploying the Yakubovich lemma. Lastly, two examples (i.e., a numerical example and the water‐quality dynamic model for the Nile River) are given to verify the efficiency of the propounded theories. © 2016 Wiley Periodicals, Inc. Complexity 21: 555–578, 2016     

Stabilization of active fault‐tolerant control systems by uncertain nonhomogeneous markovian jump models

This article investigates the stabilization and control problems for a general active fault‐tolerant control system (AFTCS) in a stochastic framework. The novelty of the research lies in utilizing uncertain nonhomogeneous Markovian structures to take account for the imperfect fault detection and diagnosis (FDD) algorithms of the AFTCS. The underlying AFTCS is supposed to be modeled by two random processes of Markov type; one characterizing the system fault process and the other describing the FDD process. It is assumed that the FDD algorithm is imperfect and provides inaccurate Markovian parameters for the FDD process. Specifically, it provides uncertain transition rates (TRs); the TRs that lie in an interval without any particular structures. This framework is more consistent with real‐world applications to accommodate different types of faults. It is more general than the previously developed AFTCSs because of eliminating the need for an accurate estimation of the fault process. To solve the stabilizability and the controller design problems of this AFTCS, the whole system is viewed as an uncertain nonhomogeneous Markovian jump linear system (NHMJLS) with time‐varying and uncertain specifications. Based on the multiple and stochastic Lyapunov function for the NHMJLS, first a sufficient condition is obtained to analyze the system stabilizability and then, the controller gains are synthesized. Unlike the previous fault‐tolerant controllers, the proposed robust controller only needs to access the FDD process, besides it is easily obtainable through the existing optimization techniques. It is successfully tested on a practical inverted pendulum controlled by a fault‐prone DC motor. © 2016 Wiley Periodicals, Inc. Complexity 21: 318–329, 2016     

Operational Matrix of Fractional Integration Based on the Shifted Second Kind Chebyshev Polynomials for Solving Fractional Differential Equations

This paper is devoted to studying a computational method for solving multi-term differential equations based on new operational matrix of shifted second kind Chebyshev polynomials. The properties of the operational matrix of fractional integration are exploited to reduce the main problem to an algebraic equation. We present an upper bound for the error in our estimation that leads to achieve the convergence rate of O(M ^−κ). Numerical experiments are reported to demonstrate the applicability and efficiency of the proposed method.

     

Temperature-assisted ionic liquid-based dispersive liquid–liquid microextraction with following back-extraction for HPLC/UV–Vis determination of 3-indole acetic acid in pea plants

In this work, the ionic liquid (IL)[C₆mim][PF₆] was used as IL-based extractant for dispersive liquid–liquid microextraction, followed by back-extraction and HPLC/UV–Vis determination of 3-indole acetic acid (IAA) in pea plant. The effects of some crucial factors such as chemical structure and volume of IL, pH adjustment, dissolution temperature, extraction time, centrifugation time, and ionic strength of aqueous sample were studied. The linear range of the HPLC method for IAA quantification was 17.5 × 10^?2–36.8 mg L^?1. LOD, LOQ, method recovery, and preconcentration factor values were 0.170 mg L^?1, 0.175 mg L^?1, 98.3, and 40 %, respectively. The RSD for the suggested method was calculated as 0.93 % at 35.04 mg L^?1 of IAA and each IL phase was able to be reused for at least four DLLME/back-extraction cycles. To evaluate the applicability of the suggested method, IAA was determined in pea plant samples.     

Insight into lattice thermal impedance via equilibrium molecular dynamics: case study on Al

Using results of equilibrium molecular dynamics simulation in conjunction with the Green–Kubo formalism, we present a general treatment of thermal impedance of a crystal lattice with a monatomic unit cell. The treatment is based on an analytical expression for the heat current autocorrelation function which reveals, in a monatomic lattice, an energy gap between the origin of the phonon states and the beginning of the energy spectrum of the so-called acoustic short-range phonon modes. Although, we consider here the f.c.c. Al model as a case example, the analytical expression is shown to be consistent for different models of elemental f.c.c. crystals over a wide temperature range. Furthermore, we predict a frequency ‘window’ where the thermal waves can be generated in a monatomic lattice by an external periodic temperature perturbation.     

Chiral selectors for enantioresolution and quantitation of the antidepressant drug fluoxetine in pharmaceutical formulations by (19)F NMR spectroscopic method

¹⁹F NMR spectroscopy was applied to the quantitative determination of fluoxetine enantiomers using different chiral recognition agents in pharmaceutical formulations. Several parameters affecting the enantioresolution including the type and concentration of chiral selector, concentration of fluoxetine and temperature were studied. The chiral selectors investigated are the cyclic oligosaccharides α-, β- and γ-cyclodextrin and a diamino derivative of methylated α-cyclodextrin (DAM-α-CD), linear polysaccharides (maltodextrin with dextrose equivalents of 4.0-7.0, 13.0-17.0 and 16.5-19.5) and the macrocyclic antibiotic vancomycin. Among the chiral selectors used, DAM-α-CD turned out to give the best resolution of the ¹⁹F NMR signals of (R)- and (S)-fluoxetine. The calibration curve was linear for (R)- and (S)-fluoxetine over the range 0.10-1.35 mg mL⁻¹, the detection limits (S/N = 3) being 5.9 and 7.5 μg mL⁻¹ for the pure solutions of (R)- and (S)-fluoxetine, respectively. The recovery studies performed on pharmaceutical samples ranged from about 90 to 110% with relative standard deviations of <8%. The results showed that the proposed method is rapid, precise and accurate. Applying statistical Student's t-test revealed insignificant difference between the real and measured contents at the 95% confidence level.     

The NIH analytical methods and reference materials program for dietary supplements

Quality of botanical products is a great uncertainty that consumers, clinicians, regulators, and researchers face. Definitions of quality abound, and include specifications for sanitation, adventitious agents (pesticides, metals, weeds), and content of natural chemicals. Because dietary supplements (DS) are often complex mixtures, they pose analytical challenges and method validation may be difficult. In response to product quality concerns and the need for validated and publicly available methods for DS analysis, the US Congress directed the Office of Dietary Supplements (ODS) at the National Institutes of Health (NIH) to accelerate an ongoing methods validation process, and the Dietary Supplements Methods and Reference Materials Program was created. The program was constructed from stakeholder input and incorporates several federal procurement and granting mechanisms in a coordinated and interlocking framework. The framework facilitates validation of analytical methods, analytical standards, and reference materials.