Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis,characterization, and investigation of their electrochemical,photochemical and computational properties

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,¹H,¹³C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)¹H and¹³C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6–31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.     

Characteristic Regimes of Transitional Separation Bubbles in Unsteady Flow

This experimental investigation deals with transition phenomena of a separated boundary layer under unsteady inlet flow conditions. The main purpose of this investigation is to understand the influence of the rotor-stator interaction in turbomachinery on the subsequent, highly loaded boundary layer. The research project is divided into two phases. In the first phase, which has been completed recently, only the variation of mean velocity caused by upstream blades was simulated in the experiments while the free-stream turbulence intensity was retained at a constant low level. The experiments are carried out in an Eifel-type wind tunnel to investigate the laminar separated boundary layer of a flat plate under oscillating inlet conditions. The adverse pressure gradient, similar to that of turbomachines, is generated by the contoured upper wall. The unsteadiness is produced by a rotating flap located downstream of the test section. The reduced frequency, the amplitude and the mean Reynolds number are varied to simulate the conditions prevailing in turbomachines. In addition to the Kelvin–Helmholtz instability of the separated shear layer, a lower frequency instability was observed. This is frequently referred to as `free shear layer flapping' and results in two distinctly different ways of re-attachment, depending primarily on the Reynolds number. For low momentum thickness Reynolds numbers at the separation point, large-scale vortices locked to the frequency of the unsteady main flow are identified. They originate nearly at the top of the separation bubble and are ejected downstream. A fully turbulent boundary layer develops after these vortices mix out. For higher Reynolds numbers, transition is completed within a short length of the free shear layer and there-attachment region. The characteristic momentum thickness Reynolds number separating these two regimes in unsteady flow is about 125. The Strouhal number (reduced frequency) does not appear to have any significant effect. Based on the experimental results, this behaviour is discussed in some detail. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural dynamics and stability analysis of 2D-FG microbeams with two-directional porosity distribution and variable material length scale parameter

Abstract

Since the two-directional functionally graded (2D-FG) materials can satisfy the new requirements raised based on the elimination of the stress concentration, delamination and cracking problems accompanying with the low cost and lightweight on the structures without sacrificing the stiffness and strength, the structural analyses of these structures become more important than ever. Moreover, the usage of the micro-electromechanical systems composed of 2D-FG materials has been increasing in automotive, military, space, biomedical, and nuclear energy industries. Within this study, the free vibration and buckling behaviors of 2D-FG porous microbeams are investigated based on the modified couple stress theory by employing a transverse shear-normal deformation beam theory and using finite element method. The effects of the thickness to material length scale parameter (MLSP) accompanying with the micro-porosity volume fraction ratio, boundary condition, aspect ratio, and gradient index on the dimensionless fundamental frequencies and dimensionless critical buckling loads of the 2D-FG porous microbeams are investigated. Moreover, with assumption of the variable material length scale parameters (VMLSP), the computed results are compared with ones obtained by employing constant MLSP. It is found that VMLSP increases the stiffness of the 2D-FG porous microbeams and effects the free vibration and buckling responses of these structures.     

Stereoconvergent Generation of a Contrasteric syn‐Bicyclopropylidene (=syn‐Cyclopropylidenecyclopropane) by Stille‐Like Coupling

Stereoisomerically pure endo‐ and exo‐7‐halo‐7‐(trimethylstannyl)benzonorcar‐3‐enes (=endo‐ and exo‐(1‐halo‐1a,2,7,7a‐tetrahydro‐1H‐cyclopropa[b]naphthalen‐1‐yl)trimethylstannane) 4 and 6 were selectively obtained by lithium? tin or magnesium? tin transmetalation in good yields (Scheme 2 and 3). The reaction of these compounds with copper(I) thiophene‐2‐carboxylate (CuTC) produced in both cases the corresponding C_S‐symmetric bicyclopropylidene (=cyclopropylidenecyclopropane) syn‐ 1 , a single diastereoisomer (Schemes 5 and 6). The structure of syn‐ 1 was undoubtedly elucidated by X‐ray single crystal diffraction. The coupling mechanism of the carbenoid cyclopropane is discussed (Scheme 7).     

Thermal decomposition kinetics of polypyrrole and its star shaped copolymer

Thermal behavior of 2,4,6-tris(4-(1H-pyrrol-1-yl)phenoxy)-1,3,5-triazine monomer, polypyrrole, and their star shaped copolymer, were investigated using TG and DTA methods. It was found that Tria melts at 517 K and after than it starts to decompose. Decomposition proceeded in two stages which were corresponding to removal of branched groups and remaining core structure degradation, respectively. Polypyrrole and copolymer showed similar thermal behaviors. These compounds decomposed in three stages which are removal of solvent, removal of dopant anion and rest of structure decomposition. The calculation of activation energies of all reactions were realized using model-free (KAS and FWO) methods. The graphs were prepared which show the alteration of activation energy with decomposition ratio. Thermal analysis results showed that dopant anion and solvent removal activation energy values for copolymer are lower than polypyrrole. Star shaped loose-packed novel structure greatly facilitates solvent and dopant anion removal from copolymer. It can be concluded also that thermal analysis can be used as predict package structure of conducting polymers.     

A probabilistic evolution approach trilogy, part 2: spectral issues for block triangular evolution matrix, singularities, space extension

This is the second part of the trilogy on the probabilistic evolution approach and related to the quantum dynamical systems as the first part is. In this sense this work extends the content of the first part to the perhaps secondary but very important details. The spectral investigation of the evolution matrix reveals important issues first and brings the importance of the zero eigenvalues to the surface. The asymptotic convergence possibility and difficulties arising from there can be softened by redefining the state vector. Beside the redefinition, the dimensional extension by adding new elements to the state vector may facilitate the utilization of evolution matrix by bringing conicality or at least multinomiality. The space extension may also help us to deal with singular Hamiltonian systems. All these issues are focused on rather phenomenologically. Illustrative or not, no comprehensive implementation is given since the main purpose is just conceptuality.     

Electrical and photoelectrical behaviour of heterojunctions based on novel oligomeric metal complexes

Naringenin‐based Schiff base ligands with 4‐aminobenzoic hydrazide were obtained as a unilateral form ( L¹ ). The ligand was oligomerized by oxidative polycondensation reaction with NaOCl as an oxidant in an aqueous alkaline medium at 90 °C to form a functional oligomer ( L² ), and its transition metal complexes such as those with Cu(II), Ni(II) and Zn(II) were prepared. The monomer and the oligomeric compounds were characterized using various techniques. Optical and electrical properties of the complexes were also investigated. All compounds showed indirect band gaps and they can be accepted as being in the semiconductor class. Organic–inorganic hybrid devices were obtained using n‐Si inorganic semiconductor and the complexes. The characteristic parameters of the devices were determined using current–voltage (I–V) and capacitance–voltage measurements in the dark. Photoelectrical properties of the devices were investigated using I–V measurements under a solar simulator with an AM1.5 global filter. Copyright © 2015 John Wiley & Sons, Ltd.