Solvation effects on cation–π interactions: a test study involving the quaternary ammonium ion

Water solvation effects on theoretical binding energies of the tetramethylammonium cation with benzene, phenol and indole have been analyzed as a prototype of biological cation– interactions. Solvent effects were introduced in the quantum chemical computations either by considering molecules belonging to the first solvation of the tetramethylammonium or by a polarizable continuum model. Our results show that the calculated binding energies are reduced by about three quarters with respect to the corresponding gas-phase results, but the sequence benzene<phenol<indole is preserved, in accordance with the concept of cation– interactions. Similar results are obtained for the interaction of tetramethylammonium with the benzene–indole pair.Contribution to the Jacopo Tomasi Honorary Issue     

Photochemical behavior of a new long-chain UV absorber derived from 4-tert-butyl-4'-methoxydibenzoylmethane

A new UV filter, the 1-(4-tert-butylphenyl)-2-decanyl-3-(4'-methoxyphenyl)-propane-1,3-dione, called C10-DBM, was prepared by grafting a 10-carbon aliphatic chain to the alpha-carbonyl position of 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM), a well-known and often used UV filter. The UV-A absorption efficiency of organic solutions containing the new filter was tested and compared with identical solutions containing BM-DBM with or without irradiation (xenon lamp). The originality of this new filter is that its UV-A absorbance appeared during irradiation of the molecule. Although the molar absorption coefficient of C10-DBM in the UV-A domain was lower than that of BM-DBM, the solutions absorption exhibited a much more photostable behavior under irradiation. In this study, we first demonstrated that C10-DBM was a precursor of BM-DBM (enol isomer) by means of high-performance liquid chromatography followed by mass spectrometry. Indeed, we showed that the UV-A absorption of C10-DBM solutions appearing during the irradiation of the molecule was due to a Norrish-II reaction (beta-cleavage), which induced the release of the BM-DBM enol form and 1-decene. Then, we established a kinetic model for the photochemistry of C10-DBM and fitted the variation of UV absorption spectra to confirm the proposed mechanism.     

Dynamic criticality in glass-forming liquids

We propose that the dynamics of supercooled liquids and the formation of glasses can be understood from the existence of a zero-temperature dynamical critical point. To support our proposal, we derive a dynamic field theory for a generic kinetically constrained model, which we expect to describe the dynamics of a supercooled liquid. We study this field theory using the renormalization group (RG). Its long time behavior is dominated by a zero-temperature critical point, which for d>2 belongs to the directed percolation universality class. Molecular dynamics simulations seem to confirm the existence of dynamic scaling behavior consistent with the RG predictions.     

Homogenization of random semilinear PDEs

We prove a homogenization result for system of semilinear parabolic PDEs of the type

Synthesis of a new polymer surface bearing grafted azo polymer chains

Azobenzene, a photosensitive chromophore that undergoes photoinduced and thermal cis–trans isomerization, can be applied in a nonlinear optical field. {4′‐[(Hydroxy)ethyl]amino}‐4‐nitroazobenzene (disperse red 1) corresponds to one of these azo compounds, which can be grafted to a polymer chain as a part of the main chain, as a dangling group, or onto the polymer surface. In the last case, disperse red 1 is transformed into an acrylic monomer and then grafted onto a polypropylene surface modified with a cold carbon dioxide‐plasma treatment. A method is proposed for quantifying the radicals formed during the plasma treatment and, consequently, for optimizing the grafting reaction. The best conditions (the nature of the solvent, temperature, monomer concentration, and duration) are given. Both IR and Raman spectroscopies were used as efficient techniques for grafting characterization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3052–3061, 2001     

A posteriori error estimator for finite volume methods

In this paper, first we discuss a technique to compare finite volume method and some well-known finite element methods, namely the dual mixed methods and nonconforming primal methods, for elliptic equations. These both equivalences are exploited to give us a posteriori error estimator for finite volume methods. This estimator is explicitly given, easy to compute and asymptotically exact without any regularity of the solution in unstructured grids.     

Comparative structural analysis of 4,5- and 3,6-dialkylsulfanylphthalonitriles of different bulkiness

Phthalonitriles disubstituted by alkylsulfanyl moieties of different bulkiness (tert-butyl, adamantly, cyclohexyl and hexyl) and in 4,5- or 3,6-positions, respectively, set A and set B, have been prepared for comparative structural analyses. Miscellaneous parameters such as melting points and related polarity of the compounds are summarized. Substituents position and bulkiness effects on NMR and IR spectroscopy as well as refined X-ray structural data were examined.     

Preparation of amphiphilic glycerol-substituted zinc phthalocyanines using copper-free Sonogashira cross-coupling in aqueous medium

Palladium-catalyzed copper-free Sonogashira cross-coupling reactions were performed on a protected and unprotected monoiodotriglycerol substituted Zn(II) phthalocyanine with various alkynes in organic and aqueous medium. From the silyl protected alkyne derivative, a protected homo coupled dimeric product was also prepared using Glaser coupling. All products were purified by reverse phase HPLC and the assigned structures were confirmed by mass and UV-vis spectroscopy.     

The semiotic and conceptual genesis of angle

ZDM – Mathematics Education - In the present study, we try to understand how students at the end of primary school conceive of angle: Is an angle a magnitude for them or a geometric figure,...