Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Production and characterization of refractive index gratings in high-birefringence fibre optics

In this work, we report production and modelling of both Bragg gratings and rocking filters in high birefringence fibre optics. Bragg gratings are produced by UV (257.0 nm) external interferometric exposition of a frequency-doubled Ar⁺ ion laser, whereas for rocking filters formation the visible Ar⁺ ion laser lines in 488.0 and 514.5 nm are used in an internal method. The spectral characteristics due to the birefringence properties are studied through numerical methods and experimental techniques. The spectral responsivity of the structures under temperature changes and stress application is presented.     

Preconcentration of trace antimony in tap and sea water on activated alumina. Determination by graphite furnace atomic absorption spectrometry

Summary A method is described for antimony preconcentration based on retention on a column of activated alumina. Recovery is 80% when no pH-control and 4 mol/l HCl as eluent are used. The preconcentration factor is 400. The method was applied to the determination of antimony in spiked tap and sea water. The analytical performance of the method is discussed.     

Sustainability in bankruptcy problems

This paper focuses on a new property for bankruptcy rules, calledsustainability, which requires that the agents with small enough claims be fully reimbursed. We show that the constrained equal-awards rule is the only rule that satisfies path independence and sustainability. Exploiting duality relations, we also provide a characterization of the constrained equal-losses rule, as the only one that satisfies composition and independence of residual claims (the dual property of sustainability).     

Synchronization Analysis of Coupled Noncoherent Oscillators

We present two different approaches to detect and quantify phase synchronization in the case of coupled non-phase coherent oscillators. The first one is based on the general idea of curvature of an arbitrary curve. The second one is based on recurrences of the trajectory in phase space. We illustrate both methods in the paradigmatic example of the R?ssler system in the funnel regime. We show that the second method is applicable even in the case of noisy data. Furthermore, we extend the second approach to the application of chains of coupled systems, which allows us to detect easily clusters of synchronized oscillators. In order to illustrate the applicability of this approach, we show the results of the algorithm applied to experimental data from a population of 64 electrochemical oscillators.     

Chelate polymers: II. Some novel transition metals complexes with azomethine‐containing siloxanes and their polyesters

New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and ¹H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd.     

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.