Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator

Our laboratory has reported the elaboration of an iterative strategy for the synthesis of dendritic macromolecules from conventional monomers. This synthetic method involves a combination of self‐regulated metal‐catalyzed living radical polymerization initiated from arenesulfonyl chlorides and an irreversible terminator multifunctional initiator (TERMINI). The previous TERMINI, (1,1‐dimethylethyl)[[1‐[3,5‐bis(S‐phenyl‐4‐N,N′ diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane, was prepared in nine reaction steps. The replacement of the previous TERMINI with one that requires only three steps for its synthesis, diethylthiocarbamic acid S‐{3‐[1‐(tert‐butyl‐dimethyl‐silanyloxy)‐vinyl]‐5‐diethylcarbamoylsulfanyl‐phenyl} ester, and the use of the more reactive Cu₂S/2,2′‐bipyridine rather than the Cu₂O/2,2′‐bipyridine self‐regulated catalyst have generated an accelerated method for the synthesis of dendritic macromolecules. This method provides rational design strategies for the synthesis of dendritic macromolecules with different compaction by the use of a single monomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4894–4906, 2005     

Studies on terbium activated yttrium based tantalate phosphors

Terbium activated yttrium niobium tantalate phosphors were prepared by solid-state reaction and were characterized by photoluminescence measurements, X-ray diffraction and scanning electron microscopy. Photoluminescence (PL) of Y_0.95Tb_0.05Ta_1?xNb_xO₄ phosphors (x = 0–1) are influenced by the host-lattice composition, degree of crystalline order and particle morphology and size. The effect of the morpho-structural properties on PL characteristics of Y(Ta,Nb)O₄:Tb powders is reported.     

Retention and selectivity tests of silica-based and metal-oxide bonded stationary phases for RP-HPLC

Chromatographic properties of silica-, zirconia- and alumina-based columns with octadecyl-, polyethylene glycol- and pentafluorophenylpropyl-bonded stationary phases were tested. Selectivities of nine columns for LC were characterized using chromatographic methods including Walters, Engelhardt, Tanaka and Galushko hydrophobicity and silanol activity tests, measurements of methylene selectivity in various aqueous-methanol and aqueous-acetonitrile mobile phases and of gradient lipophilic capacity as a measure of the effect of the sample hydrophobicity on gradient-elution separations. A semi-empirical interaction indices model, assuming a predominant role of the solvophobic interactions of test compounds with different polarities, was compared with the linear free energy relationships approach taking into account selective polar interactions. The interaction indices model was applied to both non-polar stationary phases bonded on silica, alumina and zirconia supports, and to the non-modified adsorbents in the normal-phase LC. The retention data of isomeric naphthalene disulfonic acids were used to compare the attractive and repulsive ionic interactions of the columns in purely aqueous mobile phases. The results of the hydrophobicity and polarity tests were consistent, and allowed column characterization and classification. Silanol activity was important with octadecyl silica columns, but was relatively insignificant with bonded polyethylene glycol and pentafluorophenylpropyl phases on silica gel support. Polar interactions with the alumina and zirconia support materials significantly affect the retention.     

A new algorithm that generates the image of the attractor of a generalized iterated function system

Numerical Algorithms - We provide a new algorithm (called the grid algorithm) designed to generate the image of the attractor of a generalized iterated function system on a finite dimensional space...     

Structure Results for Multiple Tilings in 3D

We study multiple tilings of 3-dimensional Euclidean space by a convex body. In a multiple tiling, a convex body $P$ is translated with a discrete multiset $\Lambda $ in such a way that each point of ${\mathbb {R}}^d$ gets covered exactly $k$ times, except perhaps the translated copies of the boundary of $P$ . It is known that all possible multiple tilers in ${\mathbb {R}}^3$ are zonotopes. In ${\mathbb {R}}^2$ it was known by the work of Kolountzakis (Discrete Comput Geom 23(4):537–553, 2000) that, unless $P$ is a parallelogram, the multiset of translation vectors $\Lambda $ must be a finite union of translated lattices (also known as quasi periodic sets). In that work (Kolountzakis, Discrete Comput Geom 23(4):537–553, 2000) the author asked whether the same quasi-periodic structure on the translation vectors would be true in ${\mathbb {R}}^3$ . Here we prove that this conclusion is indeed true for ${\mathbb {R}}^3$ . Namely, we show that if $P$ is a convex multiple tiler in ${\mathbb {R}}^3$ , with a discrete multiset $\Lambda $ of translation vectors, then $\Lambda $ has to be a finite union of translated lattices, unless $P$ belongs to a special class of zonotopes. This exceptional class consists of two-flat zonotopes $P$ , defined by the Minkowski sum of two 2-dimensional symmetric polygons in ${\mathbb {R}}^3$ , one of which may degenerate into a single line segment. It turns out that rational two-flat zonotopes admit a multiple tiling with an aperiodic (nonquasi-periodic) set of translation vectors $\Lambda $ . We note that it may be quite difficult to offer a visualization of these 3-dimensional non-quasi-periodic tilings, and that we discovered them by using Fourier methods.     

Electron-vibrational interaction in 4f-5d optical transitions in Ba, Ca, Sr thiogallates doped with Eu ions

This study is devoted to the problem of the electron-vibrational interaction in 4f-5d optical transitions. We analyze the room temperature experimental data on the vibronically assisted broad bands arising from the 4f-5d transitions in Ba, Ca, and Sr thiogallates doped with Eu²⁺ ions. An approximate simple expression is given for the shape function of the broad vibronic bands with allowance for the terms corresponding to the emission (absorption) from both ground and first excited vibrational levels. We estimate the vibronic coupling parameters and the Stokes shifts for these systems. The theoretical results are in a good agreement with the experimental data.     

An Approach to Paracyclophane-Based Tetrathiafulvalenes: Synthesis and Characterization of a Pseudo-Geminal [2.2]Paracyclophane 1,3-Dithia-2-Thione

The synthesis of paracyclophane-based tetrathiafulvalene precursors is described in the context of the importance of these compounds in the field of material chemistry. Pseudo-geminal bis(1,3-dithia-2-thione) was synthesized via the corresponding 1,3-dithiol-2-ylium salt. The latter was obtained by a synthetic procedure that involves 4,15-bis(acetyl)[2.2]paracyclophane, a new compound of interest for many researchers.     

Biomimetic Approach for Highly Selective Artificial Water Channels Based on Tubular Pillar[5]arene Dimers

Artificial water channels mimicking natural aquaporins (AQPs) can be used for selective and fast transport of water. Here, we quantify the transport performances of peralkyl-carboxylate-pillar[5]arenes dimers in bilayer membranes. They can transport ≈10⁷ water molecules/channel/second, within one order of magnitude of the transport rates of AQPs, rejecting Na⁺ and K⁺ cations. The dimers have a tubular structure, superposing pillar[5]arene pores of 5 Å diameter with twisted carboxy-phenyl pores of 2.8 Å diameter. This biomimetic platform, with variable pore dimensions within the same structure, offers size restriction reminiscent of natural proteins. It allows water molecules to selectively transit and prevents bigger hydrated cations from passing through the 2.8 Å pore. Molecular simulations prove that dimeric or multimeric honeycomb aggregates are stable in the membrane and form water pathways through the bilayer. Over time, a significant shift of the upper vs. lower layer occurs initiating new unexpected water permeation events through toroidal pores.