Effects of alcohols on micellization and on the reaction methyl 4‐nitrobenzenesulfonate + Br− in cetyltrimethylammonium bromide aqueous micellar solutions

The effects of n‐hexanol, n‐pentanol, and n‐butanol on the critical micelle concentration (cmc), on the micellar ionization degree (α), and on the rate of the reaction methyl 4‐nitrobenzenesulfonate + Br^? have been investigated in cetyltrimethylammonium bromide (CTAB) aqueous solutions. An increase in the alcohol concentration present in the solution produces a decrease in the cmc and an increase in the micellar ionization degree. Kinetic data show that the observed rate constant decreases as alcohol concentration increases. This result was rationalized by considering variations in the equilibrium binding constant of the methyl 4‐nitrobenzenesulfonate molecules to the micelles, variations in the interfacial bromide ion concentration, and variations in the characteristics of the water–alcohol bulk phase provoked by the presence of alcohols. When these operative factors are considered, kinetic data in this and other works show that the second‐order rate constants in the micellar pseudophases of water–alcohol micellar solutions are quite similar to those estimated in the absence of alcohols. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 634–641, 2004     

Configurational and conformational preferences in stereoselective acylations of <Emphasis Type="Italic">N</Emphasis>-methyl-1,3-diaminopropane with acyl chlorides

Evidence for a stereoinduction profile of the reaction of N-methyl-1,3-diaminopropane with acyl chlorides has been provided. A possibility to engage in intramolecular CH₂⋯HN and Cl⋯H-N interactions and the proton migration process to the methylamino group leads to the E secondary amides carrying the N⋯H⁺⋯N or N-H⋯N bridges, that show unusual spectroscopic images. Empirical relations between the Δδ _C chemical shift differences, the polarizability of the CO(S) groups and hydrogen bonding strength have been found. Both ¹H-¹⁵N-GHSQC and GHMBC experiments provide insight into the nature of hydrogen bonding and confirm the cyclic array of atoms.     

Chiral phase transition and Anderson localization in the instanton liquid model for QCD

We study the spectrum and eigenmodes of the QCD Dirac operator in a gauge background given by an instanton liquid model (ILM) at temperatures around the chiral phase transition. Generically we find the Dirac eigenvectors become more localized as the temperature is increased. At the chiral phase transition, both the low lying eigenmodes and the spectrum of the QCD Dirac operator undergo a transition to localization similar to the one observed in a disordered conductor. This suggests that Anderson localization is the fundamental mechanism driving the chiral phase transition. We also find an additional temperature dependent mobility edge (separating delocalized from localized eigenstates) in the bulk of the spectrum which moves toward lower eigenvalues as the temperature is increased. In both regions, the origin and the bulk, the transition to localization exhibits features of a 3D Anderson transition including multifractal eigenstates and spectral properties that are well described by critical statistics. Similar results are obtained in both the quenched and the unquenched case though the critical temperature in the unquenched case is lower. Finally we argue that our findings are not in principle restricted to the ILM approximation and may also be found in lattice simulations.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

The Low Energy Limit of String Theory and its Compactifications with Background Fluxes

String theory is consistently defined in ten dimensions. In order to extract any information about four-dimensional physics, we need to understand the properties of the six-dimensional compact manifold orthogonal to our four-dimensional universe. A possibility that is being very much explored lately is to look at manifolds on which background fluxes are turned on. In this article, we present an introduction to string theory, focusing on its massless sector. We then review traditional compactifications to four–dimensions, and finally motivate and describe the so-called flux compactifications. We interpret the allowed six-dimensional manifolds from the point of view of generalized complex geometry.     

Estimation of the aggregation number and core radius of microemulsions

Summary A simple working method for the estimation of the aggregation numbers and core radii from weight measurements of sodium bis-2-ethylhexylsulphosuccinate (aerosol-OT orAOT)/decane/water microemulsions of several compositions is proposed.Starting out from the hypotheses that (i) the density of the water inside the droplets is the same as that of free water, (ii) all the surfactant is localized as interface, and (iii) the penetration of the organic phase into the interface is negligible, values for the aggregation number and core radii comparable to those determined using more sophisticated methods were obtained.The results/methodological simplicity ratio may be of great advantage in kinetic work on reaction mechanisms in microemulsions.

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Abschätzung von Aggregationszahl und Radius von Mikroemulsionen

Zusammenfassung Es wird eine einfache Methode zur Abschätzung von Aggregationszahl und Core-Radius von Mikroemulsionen aus Gewichtsmessungen von Natriumbis-2-ethylhexylsulphosuccinat (aerosol-OT oderAOT)/Decan/Wasser-Mikroemulsionen verschiedener Zusammensetzung vorgeschlagen. Unter den Annahmen, daß (i) die Dichte von Wasser innerhalb der Aggregationen die gleiche als bei freiem Wasser ist, (ii) das ganze Emulsionsmittel in der Grenzfläche vorliegt und (iii) das Eindringen der organischen Phase in die Grenzfläche vernachlässigbar ist, können Werte für Aggregationszahlen und Core-Radien erhalten werden, die durchaus mit entsprechenden Werten aus aufwendigeren Methoden vergleichbar sind. Das Leistungsverhältnis (Ergebnisse/geringer Aufwand) ist sehr vorteilhaft und macht die Methode für kinetische Arbeiten zur Bestimmung von Reaktionsmechanismen in Mikroemulsionen interessant.

     

A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Symmetric Hilbert spaces arising from species of structures

Symmetric Hilbert spaces such as the bosonic and the fermionic Fock spaces over some lsquo;one particle space’ are formed by certain symmetrization procedures performed on the full Fock space. We investigate alternative ways of symmetrization by building on Joyal's notion of a combinatorial species. Any such species F gives rise to an endofunctor of the category of Hilbert spaces with contractions mapping a Hilbert space to a symmetric Hilbert space with the same symmetry as the species F. A general framework for annihilation and creation operators on these spaces is developed, and compared to the generalised Brownian motions of R. Speicher and M. Bożejko. As a corollary we find that the commutation relation with admits a realization on a symmetric Hilbert space whenever f has a power series with infinite radius of convergence and positive coefficients. Received: 7 April 2000; in final form: 28 November 2000 / Published online: 19 October 2001