A simple ionic triphenylene receptor for catecholamines, serotonin and D-glucosamine in buffered water

The combination of hydrophobic effects and ionic pairing within a triphenylene-based receptor were exploited for the binding of biological phenylethylamines, serotonin and D-glucosamine in phosphate buffered water.     

Core, shell, and surface-optimized dendrimers for blue light-emitting diodes

We present a novel core-shell-surface multifunctional structure for dendrimers using a blue fluorescent pyrene core with triphenylene dendrons and triphenylamine surface groups. We find efficient excitation energy transfer from the triphenylene shell to the pyrene core, substantially enhancing the quantum yield in solution and the solid state (4-fold) compared to dendrimers without a core emitter, while TPA groups facilitate the hole capturing and injection ability in the device applications. With a luminance of up to 1400 cd/m(2), a saturated blue emission CIE(xy) = (0.15, 0.17) and high operational stability, these dendrimers belong to the best reported fluorescence-based blue-emitting organic molecules.     

The two spin states of an end-on copper(II)-superoxide mimic

The reaction of nitrosobenzene with copper(I) complexes of a tetradentate ligand led to two novel species that are best described as copper(II) complexes of an O-bonded nitrosobenzyl radical anion, in either the singlet or the triplet spin-state. Both states were characterized by crystal structures, magnetic measurements and DFT calculations.     

Cationic polymerization of isobutylene at room temperature

This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Naked metal nanoparticles from metal carbonyls in ionic liquids: Easy synthesis and stabilization

An overview with more than 160 references on the synthesis and stabilization of metal nanoparticles (M-NPs) from metal carbonyls, metal salts in ionic liquids (ILs) and in particular from metal carbonyls in ionic liquids is given. The synthesis of M-NPs can proceed by chemical reduction, thermolysis, photochemical decomposition, electroreduction, microwave and sonochemical irradiation. Commercially available metal carbonyls M_x(CO)_y are elegant precursors as they contain the metal atoms already in the zero-valent oxidation state needed for M-NPs. No extra reducing agent is necessary. The side product CO is largely given off to the gas phase and removed from the dispersion. The microwave induced thermal decomposition of metal carbonyls M_x(CO)_y in ILs provides an especially rapid and energy-saving access to M-NPs because of the ILs significant absorption efficiency for microwave energy due to their high ionic charge, high polarity and high dielectric constant. The electrostatic and steric properties of ionic liquids allow for the stabilization of M-NPs without the need of additional stabilizers, surfactants or capping ligands and are highlighted by pointing to the DLVO (Derjaugin–Landau–Verwey–Overbeek) and extra-DLVO theory. Examples for the direct use of M-NP/IL dispersions in hydrogenation catalysis of cyclohexene and benzene are given.     

Euclidean algorithms are Gaussian

We obtain a central limit theorem for a general class of additive parameters (costs, observables) associated to three standard Euclidean algorithms, with optimal speed of convergence. We also provide very precise asymptotic estimates and error terms for the mean and variance of such parameters. For costs that are lattice (including the number of steps), we go further and establish a local limit theorem, with optimal speed of convergence. We view an algorithm as a dynamical system restricted to rational inputs, and combine tools imported from dynamics, such as transfer operators, with various other techniques: Dirichlet series, Perron's formula, quasi-powers theorems, and the saddle-point method. Such dynamical analyses had previously been used to perform the average-case analysis of algorithms. For the present (dynamical) analysis in distribution, we require estimates on transfer operators when a parameter varies along vertical lines in the complex plane. To prove them, we adapt techniques introduced recently by Dolgopyat in the context of continuous-time dynamics (Ann. Math. 147 (1998) 357).     

Metal particles on surfaces-desorption,optical spectra,and laser-induced size manipulation

Desorption induced by electronic excitation with laser light is discussed. Emphasis is placed on nonthermal desorption where surface plasma excitation in small particles precedes the rupture of the surface chemical bond. A scenario for the mechanism underlying such a process is proposed. In this context, calculations of the electronic spectra of small sodium particles are presented and the influence of different multipole orders of the collective electron oscillation, of different shapes of the clusters and of the substrate are outlined. Furthermore, manipulation of the size distribution of metal particles on supports is described as an application of the effect. This allows the preparation of very special surfaces with novel physical and chemical properties. Methods to characterize such adsorbate-substrate combinations, especially by use of the optical spectra of the particles, are also discussed. Finally, prospects for future experiments in this field are outlined.