A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

Sparse generalized Fourier transforms

Block-diagonalization of sparse equivariant discretization matrices is studied. Such matrices typically arise when partial differential equations that evolve in symmetric geometries are discretized via the finite element method or via finite differences. By considering sparse equivariant matrices as equivariant graphs, we identify a condition for when block-diagonalization via a sparse variant of a generalized Fourier transform (GFT) becomes particularly simple and fast. Characterizations for finite element triangulations of a symmetric domain are given, and formulas for assembling the block-diagonalized matrix directly are presented. It is emphasized that the GFT preserves symmetric (Hermitian) properties of an equivariant matrix. By simulating the heat equation at the surface of a sphere discretized by an icosahedral grid, it is demonstrated that the block-diagonalization is beneficial. The gain is significant for a direct method, and modest for an iterative method. A comparison with a block-diagonalization approach based upon the continuous formulation is made. It is found that the sparse GFT method is an appropriate way to discretize the resulting continuous subsystems, since the spectrum and the symmetry are preserved. AMS subject classification (2000)  43A30, 65T99, 20B25     

Phase-transfer agents as catalysts for a nucleophilic substitution reaction in microemulsions

The reaction between 4-tert-butylbenzyl bromide and potassium iodide was carried out in microemulsions based on different nonionic surfactants, and the reaction rates were compared with those obtained in two-phase systems with added phase-transfer agent, either a quaternary ammonium salt or a crown ether. The reactions were relatively fast in the microemulsions and extremely sluggish in the two-phase systems without additional phase-transfer agent. Addition of a phase-transfer agent did not accelerate the reaction when a hydrocarbon was used as organic solvent, neither in the two-phase system nor in the microemulsion. When a chlorinated hydrocarbon was used as solvent, phase-transfer catalysis became effective and the rate obtained in the two-phase system with an equimolar amount of phase-transfer agent added was higher than that obtained in the microemulsion. When a catalytic amount of phase-transfer agent was used, the rate in the two-phase system was about the same as the rate obtained in the microemulsion without the phase-transfer agent. The combined approach, that is, use of a microemulsion as the reaction medium and addition of a phase-transfer agent, gave the highest reaction rate. The quaternary ammonium salt (tetrabutylammonium hydrogen sulfate) was a more efficient catalyst in the microemulsion system than the crown ether ([18]crown-6).     

Adsorption of sodium dodecyl sulfate and sodium dodecyl phosphate on aluminum, studied by QCM-D, XPS, and AAS

The adsorption of two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium dodecyl phosphate (SDP), at surfaces of aluminum and aluminum oxide has been studied by means of atomic absorption spectrometry (AAS), X-ray photoelectron spectroscopy (XPS), and quartz crystal microbalance with dissipation monitoring (QCM-D). It was shown that more SDP than SDS binds to the surface and that SDP prevents dissolution of aluminum in water whereas SDS does not. This was not obvious, since the adsorption isotherms of the two surfactants to aluminum pigment powder are quite similar, as shown in an earlier work. The decreased aluminum dissolution with SDP compared to SDS was explained by the formation of a more compact protective layer with less permeability on the aluminum surface with SDP than with SDS. This is explained by differences in complexing ability between the surfactants and the aluminum pigment surface. While SDP is expected to form an inner-sphere complex with aluminum, leading to a lower accessibility of aluminum sites to water, SDS is likely to form a weaker outer-sphere complex.     

Enzymes immobilized in mesoporous silica: A physical–chemical perspective

Mesoporous materials as support for immobilized enzymes have been explored extensively during the last two decades, primarily not only for biocatalysis applications, but also for biosensing, biofuels and enzyme-controlled drug delivery. The activity of the immobilized enzymes inside the pores is often different compared to that of the free enzymes, and an important challenge is to understand how the immobilization affects the enzymes in order to design immobilization conditions that lead to optimal enzyme activity. This review summarizes methods that can be used to understand how material properties can be linked to changes in enzyme activity. Real-time monitoring of the immobilization process and techniques that demonstrate that the enzymes are located inside the pores is discussed by contrasting them to the common practice of indirectly measuring the depletion of the protein concentration or enzyme activity in the surrounding bulk phase. We propose that pore filling (pore volume fraction occupied by proteins) is the best standard for comparing the amount of immobilized enzymes at the molecular level, and present equations to calculate pore filling from the more commonly reported immobilized mass. Methods to detect changes in enzyme structure upon immobilization and to study the microenvironment inside the pores are discussed in detail. Combining the knowledge generated from these methodologies should aid in rationally designing biocatalyst based on enzymes immobilized in mesoporous materials.     

Micellar behavior in solutions of bile-acid salts

Summary The density, electrical conductivity, viscosity, lightscattering and the low-angle X-ray diffraction have been examined in the solution region of the ternary systems of sodium cholate or desoxycholate and n-decanol and water at 20°. The phase diagrams show a continuous transition from homogeneous solutions of bile-acid salt in water to homogeneous solutions of bile-acid salt and water in decanol. Along the bile-acid salt-water axis there are micellar solutions containing micelles of the normal type where the polar groups are directed outwards, and these micelles can solubilize decanol without initially undergoing any change in their basic structure. Above a critical value, however, the micellar structure is determined by the decanol molecules, and at large decanol contents there is an inversion that results in the formation of reversed micelles, with the polar groups and water now located within the core of the micelles.

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Zusammenfassung Dichte, elektrische Leitfähigkeit, Viskosität, Lichtstreuung und Kleinwinkelstreuung von Röntgenstrahlen wurden im Lösungsgebiet der ternären Systeme Natriumcholat bzw. Natriumdesoxycholat, n-Dekanol und Wasser studiert. Das Phasendiagramm zeigt einen kontinuierlichen Übergang von der homogenen Gallensalzlösung in Wasser bis zur homogenen Lösung von Gallensalz und Wasser in Dekanol. Entlang der Gallensalz-Wasserachse kommen mizellare Lösungen vor, die Mizellen vom normalen Typ enthalten, bei denen die polaren Gruppen nach außen gerichtet sind. Diese Mizellen können recht große Mengen Dekanol solubilisieren, ohne daß ihre Grundstruktur verändert wird. Oberhalb einer kritischen Menge bestimmen jedoch die Dekanolmoleküle die Mizellstruktur. Bei großen Mengen Dekanol erfolgt eine Umstrukturierung, die zur Bildung von Mizellen mit den polaren Gruppen im Mizellkern führt.

     

Synthesis of high performance,conductive PEDOT‐coated polyester yarns by OCVD technique

Production of high performance conductive textile yarn fibers for different electronic applications has become a prominent area of many research groups throughout the world. We have used oxidative chemical vapor deposition (OCVD) technique to coat flexible and high strength polyester yarns with conjugated polymer, poly(3,4‐ethylenedioxythiophene) (PEDOT) in presence of ferric (III) chloride (FeCl₃) oxidant. OCVD is an efficient solvent free technique used to get uniform, thin, and highly conductive polymer layers on different substrates. In this paper, PEDOT‐coated polyester (PET) yarns were prepared under specific reaction conditions, and the electrical, mechanical and thermal properties were compared to previously studied PEDOT‐coated viscose yarns. Scanning electron microscopy (SEM) and FT‐IR analysis revealed that polymerization of PEDOT on the surface of the polyester yarns has been taken place successfully and structural analysis showed that PEDOT has strong interactions with viscose yarns as compared to PET yarns. The voltage–current (V–I) characteristics showed that PET yarns are more conductive than PEDOT‐coated viscose yarns. The variation in the conductivity of PEDOT‐coated yarns and the heat generation properties during the flow of current through coated yarns for longer period of time, was studied by time–current (t–I) characteristics. Thermogravimeteric analysis (TGA) was employed to investigate the thermal properties and the amount of PEDOT in PEDOT‐coated PET yarns compared to PEDOT‐coated viscose. The effect of PEDOT coating and ferric (III) chloride concentration on the mechanical properties of coated yarns was evaluated by tensile testing. The obtained PEDOT‐coated conductive polyester yarns could be used in smart clothing for medical and military applications. Copyright © 2011 John Wiley & Sons, Ltd.