Four related benzazepine derivatives in a reaction pathway leading to a benzazepine carboxylic acid: hydrogen‐bonded assembly in zero,one, two and three dimensions

(2R*,4S*)‐Methyl 2,3,4,5‐tetrahydro‐1,4‐epoxy‐1H‐benz[b]azepine‐2‐carboxylate, C₁₂H₁₃NO₃, (I), and its reduction product (2R*,4S*)‐methyl 4‐hydroxy‐2,3,4,5‐tetrahydro‐1H‐benz[b]azepine‐2‐carboxylate, C₁₂H₁₅NO₃, (II), both crystallize as single enantiomers in the space group P2₁2₁2₁, while the hydrolysis product (2RS,4SR)‐4‐hydroxy‐2,3,4,5‐tetrahydro‐1H‐benz[b]azepine‐2‐carboxylic acid, C₁₁H₁₃NO₃, (III), and the lactone (2RS,5SR)‐8‐(trifluoromethoxy)‐5,6‐dihydro‐1H‐2,5‐methanobenz[e][1,4]oxazocin‐3(2H)‐one, C₁₂H₁₀F₃NO₃, (IV), both crystallize as racemic mixtures in the space group P2₁/c. The molecules of compound (IV) are linked into centrosymmetric R₂²(10) dimers by N—H...O hydrogen bonds, and those of compound (I) are linked into chains by C—H...π(arene) hydrogen bonds. A combination of O—H...O and O—H...N hydrogen bonds links the molecules of compound (III) into sheets containing equal numbers of R₄⁴(14) and R₄⁴(26) rings, and a combination of C—H...π(arene) hydrogen bonds and three‐centre O—H...(N,O) hydrogen bonds links the molecules of compound (II) into a three‐dimensional framework structure. Comparisons are made with some related compounds.     

Solving a multiobjective location routing problem with a metaheuristic based on tabu search. Application to a real case in Andalusia

In this work we present a multiobjective location routing problem and solve it with a multiobjective metaheuristic procedure. In this type of problem, we have to locate some plants within a set of possible locations to meet the demands of a number of clients with multiple objectives. This type of model is used to solve a problem with real data in the region of Andalusia (Spain). Thus, we study the location of two incineration plants for the disposal of solid animal waste from some preestablished locations in Andalusia, and design the routes to serve the different slaughterhouses in this region. This must be done while taking into account certain economic objectives (start-up, maintenance, and transport costs) and social objectives (social rejection by towns on the truck routes, maximum risk as an equity criterion, and the negative implications for towns close to the plant).     

Relative acidities and structure analysis of cis and trans isomers of 1,5‐oxazaspiro[5.5] undecane derivatives by multinuclear magnetic resonance

The relative acidities of the cis and trans isomers of a series of 1,5‐oxazaspiro[5.5]undecane derivatives were determined by measuring ΔpK in acid‐base titrations followed by ¹ H NMR. Relative structural stabilities were determined by measuring substituent chemical shift and γ‐gauche effects in ¹³C, ¹⁵N, and ¹⁷O NMR. Crystallographic characterization of a model spiro[5.5]undecane is presented to support the basicity in solid state. Copyright © 2010 John Wiley & Sons, Ltd.     

Sampling Theorem and Discrete Fourier Transform on the Riemann Sphere

Using coherent-state techniques, we prove a sampling theorem for Majorana’s (holomorphic) functions on the Riemann sphere and we provide an exact reconstruction formula as a convolution product of N samples and a given reconstruction kernel (a sinc-type function). We also discuss the effect of over- and under-sampling. Sample points are roots of unity, a fact which allows explicit inversion formulas for resolution and overlapping kernel operators through the theory of Circulant Matrices and Rectangular Fourier Matrices. The case of band-limited functions on the Riemann sphere, with spins up to J, is also considered. The connection with the standard Euler angle picture, in terms of spherical harmonics, is established through a discrete Bargmann transform.      

Analytical Solution for Multi-Species Contaminant Transport Subject to Sequential First-Order Decay Reactions in Finite Media

Transport equations governing the movement of multiple solutes undergoing sequential first-order decay reactions have relevance in analyzing a variety of subsurface contaminant transport problems. In this study, a one-dimensional analytical solution for multi-species transport is obtained for finite porous media and constant boundary conditions. The solution permits different retardation factors for the various species. The solution procedure involves a classic algebraic substitution that transforms the advection-dispersion partial differential equation for each species into an equation that is purely diffusive. The new system of partial differential equations is solved analytically using the Classic Integral Transform Technique (CITT). Results for a classic test case involving a three-species nitrification chain are shown to agree with previously reported literature values. Because the new solution was obtained for a finite domain, it should be especially useful for testing numerical solution procedures.     

Solvent and temperature effects on the conformational equilibria of a dihydrobenzo[h]quinolinium fluoroborate

Spectra of the N‐phenyl‐5,6‐dihydro‐2,4‐diphenylbenzo[h]quinolinium tetrafluoroborate (1) and of the N‐phenyl‐5,6,8,9‐tetrahydro‐7‐phenyldibenzo[c,h]acridinium tetrafluoroborate (2) were recorded in various solvents and temperatures. The analysis of the ¹H‐NMR spectra of the tetrafluoroborate salt 1, recorded in acetone, acetonitrile, 1,1,2,2‐tetrachloroethane and chloroform, revealed the existence of an equilibrium between two conformers in solution. Tight ion‐pairing in chloroform led to a smaller barrier for interconversion between the two conformers. In more polar solvents, where the dihydrobenzoquinolinium exists as a free cation, theoretical calculations predicted larger barriers. The spectra of 1 in 1,1,2,2‐tetrachloroethane also varied with temperature, resembling at higher temperatures the spectrum in CDCl₃ and at 300K spectra in more polar media. Spectra of 2 did not vary with the solvent or the temperature, in an indication of a much higher barrier to conformational interconversion, because of a greater steric hindrance between the N‐phenyl substituent and the dihydrobenzo rings. Copyright © 2009 John Wiley & Sons, Ltd.     

Dihydroquinoline derivative as a potential anticancer agent: synthesis,crystal structure,and molecular modeling studies

Molecular Diversity - Cancer is one of the leading causes of death worldwide and requires intense and growing research investments from the public and private sectors. This is expected to lead to...     

Experimental and kinetic modeling study of oxidation of acetonitrile

Oxidation of acetonitrile has been studied in a flow reactor in the absence and presence of nitric oxide. The experiments were conducted at atmospheric pressure in the temperature range 1150–1450 K, varying the excess air ratio from slightly fuel-lean to very lean. Oxidation of CH₃CN was slow below 1300 K. Nitric oxide, hydrogen cyanide and nitrous oxide were detected as important products. A detailed chemical kinetic model for oxidation of acetonitrile was developed, based on a critical evaluation of data from literature. The rate coefficients for the reactions of CH₃CN and CH₂CN with O₂ were calculated from ab initio theory. Modeling predictions were in satisfactory agreement with experiments. Calculations were sensitive to thermal dissociation of CH₃CN and to the branching fraction for CH₃CN + OH to CH₂CN + H₂O and HOCN + CH₃, respectively. More work is desirable for these steps, as well as for reactions of CH₂CN and HCCN.     

Agricultural valorisation of de-inking paper sludge as organic amendment in different soils

The objective of this study is to study the influence of de-inking paper sludge (DPS) and sewage sludge (SL) mixtures addition at different rates (2, 4 and 8%) in two soils. Incubation experiments were performed during 60 days and the influence of treatments in physical soil properties was determined by soil porosity and stability of aggregates. Differential thermal analysis (DTA) of amended soils after incubation was performed. Experimental results show that amendment increased biological soil activity, soil porosity and stability of aggregates. DTA analysis shows that the first exothermic peak generally increases with the dosage of DPS:SL due to the addition of immature organic matter. Moreover, the second peak enlarges probably due to the humification process during incubation.     

Generalization of Carré equation

The present work offers new equations for phase evaluation in measurements. Several phase shifting equations with an arbitrary but constant phase shift between captured intensity signs are proposed. The equations are similarly derived as the so-called Carré equation. The idea is to develop a generalization of Carré equation that is not restricted to four images. Errors and random noise in the images cannot be eliminated, but the uncertainty due to their effects can be reduced by increasing the number of observations. An experimental analysis of the mistakes of the technique was made, as well as a detailed analysis of mistakes of the measurement. The advantages of the proposed equation are its precision in the measures taken, speed of processing and the immunity to noise in signs and images.