Ring chain transformation of γ-keto-δ-crotonolactones: A convenient synthesis of 1,4-piperazinones, 1,4-thiazinones and 1,4-diazepinones

A new procedure for the efficient synthesis of 1,4-piperazinones, 1,4-thiazinones and 1,4-diazepinones is presented. The reaction is based on a ring chain transformation of γ-keto-δ-crotonolactones induced by 1,2- or 1,3-diamino- (or thiamino-) binucleophiles. The reaction sequence of this transformation is also discussed.     

Modeling of contaminant transport resulting from dissolution of nonaqueous phase liquid pools in saturated porous media

A mathematical model for transient contaminant transport resulting from the dissolution of a single component nonaqueous phase liquid (NAPL) pool in two-dimensional, saturated, homogeneous porous media was developed. An analytical solution was derived for a semi-infinite medium under local equilibrium conditions accounting for solvent decay. The solution was obtained by taking Laplace transforms to the equations with respect to time and Fourier transforms with respect to the longitudinal spatial coordinate. The analytical solution is given in terms of a single integral which is easily determined by numerical integration techniques. The model is applicable to both denser and lighter than water NAPL pools. The model successfully simulated responses of a 1,1,2-trichloroethane (TCA) pool at the bottom of a two-dimensional porous medium under controlled laboratory conditions.Notation a,a ₁ defined in (45a) and (45b), respectively - b defined in (45c) - b vector of true model parameters (n×1) - vector of estimated model parameters (n×1) - c liquid phase solute concentration (solute mass/liquid volume), M/L³ - c _s aqueous saturation concentration (solubility), M/L³ - C dimensionless liquid phase solute concentration, equal toc/c _s - molecular diffusion coefficient, L²/t - ^e effective molecular diffusion coefficient, equal to / ^*, L²/t - D _x longitudinal hydrodynamic dispersion coefficient, L²/t - D _z hydrodynamic dispersion coefficient in the vertical direction, L²/t - e random vector with zero mean (m×1) - erf[x] error function, equal to (2/ ^1/2) - f vector of fitting errors or residuals (m×1) - Fourier operator - _-1 Fourier inverse operator - g vector of model simulated data (m×1) - k mass transfer coefficient, L/t - average mass transfer coefficient, L/t - K _d partition or distribution coefficient (liquid volume/solids mass), L³/M - pool length, L - _o distance between the pool and the origin of the specified Cartesian coordinate system, L - Laplace operator - _-1 Laplace inverse operator - m number of observations - M Laplace/Fourier function defined in (38) - n number of model parameters - N Laplace/Fourier function defined in (39) - p defined in (46) - Pe _x Péclet number, equal toU _x /D _x - Pe _z Péclet number, equal toU _x /D _z - q defined in (47) - R retardation factor - s Laplace transform variable - S objective function - Sh local Sherwood number, equal tok/ _e - Sh _o overall Sherwood number, equal to l/ _e - t time,t - T dimensionless time, equal toU _x t/ - u dummy integration variable - u vector of independent variables - U _x average interstitial velocity, L/t - x spatial coordinate in the longitudinal direction, L - X dimensionless longitudinal length, equal to (x–)/ - y vector of observed data (m×1) - z spatial coordinate in the vertical direction, L - Z dimensionless vertical length, equal toz/ - Fourier transform variable - defined in (37) - defined in (50) - porosity (liquid volume/aquifer volume), L³/L³ - defined in (52a) and (52b), respectively - decay coefficient, t^–1 - dimensionless decay coefficient, equal to /U _x - bulk density of the solid matrix (solids mass/aquifer volume), M/L³ - dummy integration variable - ^* tortuosity     

An analytical model for the determination of the cup-burner minimum extinguishing concentration of inert fire suppression agents

An analytical model based on the perfectly stirred reactor (PSR) concept is developed and utilized in the prediction of the minimum extinguishing concentration (MEC) of inert fire suppression agents that is established in the standard cup-burner test. In the PSR-based approach, both thermal (heat absorption) and chemical mechanisms of fire suppression can be captured. The assumed perfect mixing, on the other hand, prevents the ability to capture transport related mechanisms. In past work, the PSR approach using detailed chemistry was demonstrated to be effective in reproducing the MEC albeit with the need of single point calibration. The closed form solution presented herein becomes possible when the detailed chemistry is simplified to a single step, mole preserving chemical reaction. At the core of the model is an analytical expression for the extinction temperature which is transcendental and thus requires a numerical iterative solution. The analytical model is first verified using a traditional computational PSR (CHEMKIN package) that employs the same reduced kinetics as the analytical model. Subsequently, results from the analytical model are contrasted to those from a traditional PSR with detailed chemistry, from a semi-analytical approach that assumes heat absorption by the agent is the primary extinguishing mechanism, and from experimental data of various research groups. Good agreement is achieved validating the analytical model as a simple and accurate approach to determine the MEC. The analytical model is also used in a parametric assessment of the impact of geographic altitude (i.e. effect of ambient pressure) on the MEC and results are in good agreement with those of a traditional PSR with detailed chemistry.     

Sesquiterpenes from Chrysoma Pauciflosculosa

Abstract

The aerial parts of Chrysoma pauciflosculosa (syn. Solidago pauciflosculosa) gave two new sesquiterpenes, (+)-β-turmerone and a bisabolane endoperoxide, together with the known (-)-α-trans-bergamotene and (+)-β-sesquiphellandrene. When exposed to air and light, (+)-β-turmerone and (+)-β-sesquiphellandrene gave oxidative degradation products, involving hydroperoxide intermediates. Photosensitized singlet oxygen reactions of (+)-β-turmerone provided a series of bisabolane-type endoperoxides. The structures of the natural compounds as well as those of the degradation products and derivatives were elucidated by chemical and spectroscopic methods, mainly NMR and MS. Aqueous solutions of (+)-β-turmerone,(+)-β-sesquiphellandrene and (-)-α-trans-bergamotene were tested for their effects on the germination and radicle growth of three Florida sandhill species, Rudbeckia hirta, Schizachyrium scoparium, Leptochloa dubia, as well as Lactuca sativa. (+)-β-Turmerone significantly inhibited germination of L. sativa, stimulated radicle growth of L. sativa and S. scoparium at the 10^?4 M level, and mildly inhibited radicle growth of R. hirta, as did (+)-β-sesquiphellandrene. (-)-α-trans-Bergamotene stimulated germination of S. scoparium and L. sativa and significantly enhanced radicle growth of S. scoparium.     

Comparative studies of localized buckling in sandwich struts with different core bending models

Analytical models with geometric non-linearities accounting for interactions between local and global instability modes leading to localized buckling in sandwich struts are formulated. For the core material response, two increasingly sophisticated bending models are compared against each other: Timoshenko beam theory (TBT) and Reddy-Bickford beam theory (RBT). Numerical solutions of the analytical models are validated with the commercial finite element code ABAQUS. It is found that there is a small but significant difference in the critical load between the two models and that the previously obtained solution slightly underestimates the linear buckling strength. More importantly, it is found that the RBT model predicts the onset of interactive buckling before the TBT model and, according to the results from the finite element study, matches the actual behaviour of a strut in both its initial and advanced post-buckling states with excellent correlation.     

Effect of Local DBD Plasma Actuation on Transition in a Laminar Separation Bubble

This work examines the effect of local active flow control on stability and transition in a laminar separation bubble. Experiments are performed in a wind tunnel facility on a NACA 0012 airfoil at a chord Reynolds number of 130 000 and an angle of attack of 2 degrees. Controlled disturbances are introduced upstream of a laminar separation bubble forming on the suction side of the airfoil using a surface-mounted Dielectric Barrier Discharge plasma actuator. Time-resolved two-component Particle Image Velocimetry is used to characterise the flow field. The effect of frequency and amplitude of plasma excitation on flow development is examined. The introduction of artificial harmonic disturbances leads to significant changes in separation bubble topology and the characteristics of coherent structures formed in the aft portion of the bubble. The development of the bubble demonstrates strong dependence on the actuation frequency and amplitude, revealing the dominant role of incoming disturbances in the transition scenario. Statistical, topological and linear stability theory analysis demonstrate that significant mean flow deformation produced by controlled disturbances leads to notable changes in stability characteristics compared to those in the unforced baseline case. The findings provide a new outlook on the role of controlled disturbances in separated shear layer transition and instruct the development of effective flow control strategies.     

Hierarchical distributed metamodel‐assisted evolutionary algorithms in shape optimization

In aerodynamic shape optimization, the availability of multiple evaluation models of different precision and hence computational cost can be efficiently exploited in a hierarchical evolutionary algorithm. Thus, in this work the demes of a distributed evolutionary algorithm are ordered in levels, with each level employing a different flow analysis method, giving rise to a hierarchical distributed scheme. The arduous task of exploring the design space is undertaken by demes consisting the lower hierarchy level, which use a low‐cost flow analysis tool, namely a viscous–inviscid flow interaction method. Promising solutions are directed towards the higher level, where these are further evolved based on a high precision/cost evaluation tool, viz. a Navier–Stokes equations solver. The final, optimal solution is obtained from the highest hierarchy level. At each level, metamodels, trained on‐line on the outcome of evaluations with the level's analysis tool, are used. The role of metamodels is to allow a parsimonious use of computational resources by filtering the poorly performing individuals in each deme. The entire algorithm has been implemented so as to take advantage of a parallel computing system. The efficiency and effectiveness of the proposed hierarchical distributed evolutionary algorithm have been assessed in the design of a transonic isolated airfoil and a compressor cascade. Remarkable superiority over the conventional evolutionary algorithms has been monitored. Copyright © 2006 John Wiley & Sons, Ltd.     

Thiocarbonyls. X. The Isomeric 2,4,6-Tris(halophenyl)-1,3,5-thianes

Nine pairs of isomeric 2,4,6-tris(halophenyl)-1,3,5-trithianes have been assayed in the crude state by n.m.r. techniques, and separated and purified by chromatography. Contrary to previous reports, the α-(cis, trans)-isomers are the major products in most cases. These compounds are shown to exist as puckered chair trithiane structures, even in the more hindered α-(cis, trans)-o-halophenyl cases, by the clear resolution of axial and equatorial trithiane ring protons in a ratio of 2:1. An o-halogen on an axial phenyl group in the α-isomers causes the aromatic group to exert an anisotropic deshielding effect on adjacent axial protons, so as to cause the axial and equatorial proton peaks to appear as a singlet in some solvents. Melting point differences, in several cases quite large, from those previously reported have been observed for six of the eighteen triaryltrithianes reported.     

Dynamic thermoelastic effects for half-planes and half-spaces with nearly-planar surfaces

The effects of non-planarity on the dynamic surface temperature changes induced for plane-strain and 3D problems on the nearly-planar surfaces of, respectively, coupled thermoelastic half-planes and half-spaces by surface heat fluxes are treated. The nearly-planar nature of the surfaces allows the problem solutions to be written, following a standard perturbation scheme, as series expansions in a dimensionless surface contour amplitude parameter. The first, or zero-order, terms represent the ideal (planar) surface solutions, while the second, or first-order, terms represent corrections for non-planarity.Because the characteristic thermoelastic time is of O(10^–7)s, large-time asymptotic forms of the exact integral transform solutions can be used. These can be inverted exactly and used in Green's function operations to yield analytic, or integrals of analytic, expressions. Two types of thermal loading for the half-plane and yet a third type of thermal loading for the half-space are considered. Comparison of the zero- and first-order surface temperature changes for each case indicate that non-planarity gives rise for large times to changes in surface regions beyond those predicted by an ideal surface analysis. Moreover, the magnitudes of these changes can be more significant than the ideal surface results.