Isotope effects on the microphase separation of paraffin mixtures

Isotopic sensitivity is reported in both the formation and the above ambient temperature annealing behaviour of lamellar microphases in C₃₀:C₃₆ paraffin solid solutions. The time resolved small angle neutron scattering from a 1:1 C₃₀H₆₂:C₃₆D₇₄ mixture and its complementary pair 1:1 C D :C H has been studied. Upon quenching such mixtures from the melt; the solid solution so formed nucleates spontaneously to a ‘long period’ microphase. The two systems differ in that for 1:1 C₃₀D₆₂:C₃₆H₇₄ there is also strong diffraction at Q = 0·136 A^-1 associated with C₃₆H₇₄ enrichment of the solid solution or a separate phase. Both processes are sensitive to the isotopic composition of the mixture. For both systems the long period scattering from a quenched liquid mixture develops in periods of hours at ambient temperature. Heating the aged microphase structures to temperatures above about 43°C causes them to disappear, but again isotropic sensitivity is noted. It is concluded that the effects are largely kinetic in origin, in agreement with earlier IR studies on intralamellar microaggregation in this system.     

Synthesis, Structure and Alkali Metal Ion Binding Properties of a Podand Polyether Derived from Calix[4]arene, 5,11,17,23-tetra-tert-butyl-25,27-di(phenylmethoxy)-26,28-di(2‘-methoxyethoxy)-calix[4]arene

The ligand 5,11,17,23-tetra-t-butyl-25,27-di(phenylmethoxy)-26,28-di(2-methoxy-ethoxy)calix[4]arene,designed as an analogue of some calixcrown speciesin order to evaluate possible origins of their selectivity in alkali metal ion binding, has been synthesised and structurally characterised by X-ray crystallography. The crystals are monoclinic, P21/n, a = 15.940(6), b = 19.388(5), c = 20.020(5) Å, = 109.10(2) deg., Z = 4, conventional R on |F| being 0.073 for 3454 independent, observed (I > 3(I)) reflections. 1H-NMR studies in 1:1 CD3CN/CDCl3solvent have shown that the ligand exerts a strong preference for the lighteralkali metal ions (Li+ and Na+) contrary to the binding behaviour of knowncalixcrowns. This may reflect interactions restricted to the lower rim donor atoms without concomitant interaction with the calixarene -electrons, perhaps because the latter interactions are substituted by those with the benzyl group -electrons.     

ANALOGS AND DERIVATIVES OF FIREFLY OXYLUCIFERIN, THE LIGHT EMITTER IN FIREFLY BIOLUMINESCENCE

Abstract— The 5-methyl analog of firefly oxyluciferin, two isomeric O-methyl ether derivatives of it and an O, O Ó-dimethyl ether derivative were synthesized and their UV absorption and fluorescence emission spectra were determined. Comparisons of the emission data with the emission wavelength in bioluminescence indicate that the mono-anions of firefly oxyluciferin are candidates for the light-emitters in bioluminescence. Further, we have found that the chemiluminescence of active esters of firefly luciferin produces (from the keto form of oxyluciferin) only red light emission under a variety of conditions; a yellow-green light emission (from the enolic forms of the oxyluciferin product) could not be elicited.     

Lattice Forces in Heavy Metal Picrates: Structural Characterization of Lead and Mercury Species

Structure determinations for the dimethylsulfoxide (dmso) solvate of lead(II) picrate (picrate = pic = 2,4,6-trinitrophenoxide), formally a centrosymmetric dimer, [Pb₂(dmso)₄(pic)₄], and for unsolvated mercury(I) picrate, a polymer of conventional mercurous dimers, [Hg₂(pic)₂] _n , show that, despite considerable differences in the form of the metal unit, there are remarkable similarities in the mode of coordination of the bridging picrate ligands. In both lattices, parallel arrays of picrate rings can be discerned but appear to be associated with short N…O, O…O or O…C contacts rather than C…C. In the Pb compound, there is also evidence of intramolecular contacts to dmso-S.     

IMPROVEMENT OF THE SEMI-ANALYTICAL METHOD, FOR DETERMINING THE GEOMETRICALLY NON-LINEAR RESPONSE OF THIN STRAIGHT STRUCTURES. PART I: APPLICATION TO CLAMPED-CLAMPED AND SIMPLY SUPPORTED-CLAMPED BEAMS

In a previous series of papers (Benamar 1990 Ph.D. Thesis, University of Southampton; Benamaret al. 1991 Journal of Sound and Vibration149, 179-195;164, 399-424 [1-3]) a general model based on Hamilton's principle and spectral analysis has been developed for non-linear free vibrations occurring at large displacement amplitudes of fully clamped beams and rectangular homogeneous and composite plates. The results obtained with this model corresponding to the first non-linear mode shape of a clamped-clamped (CC) beam and to the first non-linear mode shape of a CC plate are in good agreement with those obtained in previous experimental studies (Benamaret al. 1991 Journal of Sound and Vibration 149, 179-195;164, 399-424 [2, 3]). More recently, this model has been re-derived (Azar et al. 1999 Journal of Sound and Vibration224, 377-395; submitted [4, 5]) using spectral analysis, Lagrange's equations and the harmonic balance method, and applied to obtain the non-linear steady state forced periodic response of simply supported (SS), CC, and simply supported-clamped (SSC) beams. The practical application of this approach to engineering problems necessitates the use of appropriate software in each case or use of published tables of data, obtained from numerical solution of the non-linear algebraic system, corresponding to each problem. The present work was an attempt to develop a more practical simple “multi-mode theory” based on the linearization of the non-linear algebraic equations, written on the modal basis, in the neighbourhood of each resonance. The purpose was to derive simple formulae, which are easy to use, for engineering purposes. In this paper, two models are proposed. The first is concerned with displacement amplitudes of vibrationW_max /H, obtained at the beam centre, up to about 0·7 times the beam thickness and the second may be used for higher amplitudes W_max/H up to about 1·5 times the beam thickness. This new approach has been successfully used in the free vibration case to the first, second and third non-linear modes shapes of CC beams and to the first non-linear mode shape of a CSS beam. It has also been applied to obtain the non-linear steady state periodic forced response of CC and CSS beams, excited harmonically with concentrated and distributed forces.