Novel metallophthalocyanines bearing 3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,4-triazole bulky substituents by microwave irradiation

The synthesis of metallophthalocyanines [6–9; M = Ni(II), Zn(II), Co(II) and Cu(II)] with four 1,2,4-triazole units obtained from 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-methylphenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile (5) in the presence of dimethylaminoethanol and the corresponding anhydrous metal salts is described. The thermal stabilities of the Pc compounds were determined by thermogravimetric analysis. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis.     

TRANSIENT SIMULATION OF INTERNAL SEPARATED FLOWS USING AN INTELLIGENT HIGHER-ORDER SPATIAL DISCRETIZATION SCHEME

This paper summarizes the method-of-lines (MOL) solution of the Navier–Stokes equations for an impulsively started incompressible laminar flow in a circular pipe with a sudden expansion. An intelligent higher-order spatial discretization scheme, which chooses upwind or downwind discretization in a zone-of-dependence manner when flow reversal occurs, was developed for separated flows. Stability characteristics of a linear advective–diffusive equation were examined to depict the necessity of such a scheme in the case of flow reversals. The proposed code was applied to predict the time development of an impulsively started flow in a pipe with a sudden expansion. Predictions were found to show the expected trends for both unsteady and steady states. This paper demonstrates the ease with which the Navier–Stokes equations can be solved in an accurate manner using sophisticated numerical algorithms for the solution of ordinary differential equations (ODEs). Solutions of the Navier–Stokes equations in primitive variables formulation by using the MOL and intelligent higher-order spatial discretization scheme are not available to date. © 1997 by John Wiley & Sons, Ltd.     

Measurement of ambient fluid entrainment during laminar vortex ring formation

Planar laser induced fluorescence (PLIF) and digital particle image velocimetry (DPIV) combined with Lagrangian coherent structure (LCS) techniques are utilized to measure ambient fluid entrainment during laminar vortex ring formation and relate it to the total entrained volume after formation is complete. Vortex rings are generated mechanically with a piston-cylinder mechanism for a jet Reynolds number of 1,000, stroke ratios of 0.5, 1.0 and 2.0, and three velocity programs (Trapezoidal, triangular negative and positive sloping velocity programs). The quantitative observations of PLIF agree with both the total ring volume and entrainment rate measurements obtained from the DPIV/LCS hybrid method for the jet Reynolds number of 1,000, trapezoidal velocity program and stroke ratio of 2.0 case. In addition to increased entrainment at smaller stroke ratios observed by others, the PLIF results also show that a velocity program utilizing rapid jet initiation and termination enhances ambient fluid entrainment. The observed trends in entrainment rate and final entrained fluid fraction are explained in terms of the vortex roll-up process during vortex ring formation.     

Reactions of Enaminones with Diazocarbonyl Compounds

The [Cu(acac)₂]‐catalyzed reactions of several tertiary enaminones with three diazocarbonyl compounds, i.e., dimethyl diazomalonate, ethyl diazoacetoacetate, and ethyl diazoacetate, yielded amino‐ and additionally carbonyl‐substituted dihydrofurans, together with further furan derivatives. Due to the conjugation of α‐carbonyl/α‐Ph groups, reactions proceeded only via 1,5‐electrocyclization of corresponding keto‐ylides. On the other hand, in the absence of any α‐substituent, tertiary enaminone and ethyl diazoacetate, reacted via an accompanying mechanism by a push‐pull cyclopropane intermediate, to yield a 2,4‐dicarbonyl‐substituted furan in one step with moderate yield.     

Carbonyl ylide reactions of α-benzylidene-β-dicarbonyl compounds: competitive formation of dihydrofurans and dihydrobenzoxepines

α-Benzylidene-β,β′-biscarbonyl compounds were reacted with dimethyl diazomalonate using Cu(II) acetylacetonate as a catalyst. Dihydrofurans or mixtures of dihydrofurans and dihydrobenzoxepines were obtained depending on the nature of the carbonyl group present in the starting material.     

Reactions of α,β‐Enones with Diazo Compounds,Part 3

Carbonyl ylides arising from ethyl acetodiazoacetate/dimethyl diazomalonate and α,β‐enones with mainly s‐cis conformations underwent disrotatory cyclization to produce dihydrofuran derivatives. This process proved to be sensitive to steric effects. The corresponding ylides arising from rather s‐trans α,β‐enals yielded dioxole derivatives. The mechanisms of the reactions are discussed.     

Broad band metamaterial absorber based on wheel resonators with lumped elements for microwave energy harvesting

A new metamaterial absorber structure is designed and characterized both numerically and experimentally for microwave energy harvesting applications. The proposed structure includes four wheel resonators with different dimensions, from which the overall response of the structure can then be obtained by summing all the overlapping frequency responses corresponding to each dimension. The essential operation frequency range of the wheels is selected in such a way that the energy used in wireless communications and found within the environment that we live is absorbed. The dimensions are obtained using parametric study and genetic algorithm to realize wideband absorption response. When the simulation and measurement results are taken into account, it is observed that the metamaterial absorber based harvester has potential to absorb and convert microwave energy with an absorption ratio lying within the range of 80 and 99% for the frequency band of 3–5.9 and 7.3–8 GHz. The conversion efficiency of the structure as a harvester is found to be greater than 0.8 in the interval of 2–5 GHz. Furthermore, the incident angle and polarization dependence of the wheel resonator based metamaterial absorber and harvester is also investigated and it is observed that the structure has both polarization and incident angle independent frequency response with good absorption characteristics in the entire working frequency band. Hence, the suggested design having good absorption, polarization and angle independent characteristics with wide bandwidth is a potential candidate for future energy harvester using wireless communication frequency band.     

Poly(trifluoroethylene) adsorption and heterogeneous photochlorination reactions

Heterogeneous (gas-solid) photochlorination reactions of poly(trifluoroethylene) (PF 3E) films were studied as a function of reaction time and light intensity. The rate of chlorination was found to be faster in high-intensity light when compared to the reaction in ambient light. PF 3E irreversibly adsorbed to oxidized silicon and covalently attached amine monolayers supported on silicon, producing hydrophobic thin films in the thickness range of 8-40 A. Adsorption conditions such as polymer concentration and solvent composition were investigated. Radical grafting of maleic anhydride to the polymer backbone resulted in increased adsorption on oxidized silicon.