Investigation of the complexation behaviour and catalysis of IBiox-[(−)-menthyl]·HOTf

Herein we provide an overview on the unique properties of the sterically demanding IBiox-[(?)-menthyl]?HOTf ligand (such as flexibility and sterics) and an application of this ligand in Pd-catalyzed asymmetric intra- and intermolecular α-arylation reactions. Furthermore we demonstrate the synthesis of novel NHC–metal complexes and a new bifunctional NHC ligand whilst insight into the mechanistic mode of action of IBiox-[(?)-menthyl]?HOTf in catalysis is provided.     

Encapsulants for light‐emitting diodes from visible light‐cured epoxy monomers

During the last decade, light‐emitting diodes (LEDs) have replaced incandescent, fluorescent, and neon lamps due to their ability to produce high luminosity at low currents and voltages. LEDs are currently encapsulated by thermally curable epoxy resins. However, long periods of curing at high temperature result in high consumption of energy and require stringent process control to avoid failure of the devices. In addition, the thermal cure results in yellowing of the encapsulant, which decreases the efficiency of the LED. In recent years, photoinitiated polymerization has received much interest as it congregates a wide range of economic and ecological benefits. Cationic photoinitiators, such as diaryliodonium salts, generate Brønsted acid in situ, which initiates polymerization. The process can be triggered on demand by irradiating the mixture with light. Results from the present research reveal that cycloaliphatic epoxy monomers, photoactivated with an iodonium salt and Camphorquinone, polymerize readily under visible light irradiation (470 nm) in the absence of external heating. The partial replacement of cycloaliphatic epoxy with aromatic diglycidyl ether of bisphenol‐A (DGEBA) is an effective means of improving the refractive index of the material and consequently the efficiency of the photoemission. Visible light polymerization of DGEBA pure proceeds at a slow rate; however, it is enhanced by the increase in temperature during the polymerization of the highly reactive cycloaliphatic monomer. From results obtained in the present research, it may be concluded that visible light polymerization of epoxy monomers is a promising route for the processing of LED encapsulants. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermally Induced Growth of ZnO Nanocrystals on Mixed Metal Oxide Surfaces

An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG‐MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH₄NO₃). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X‐ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate.     

Tail asymptotics for the sum of two heavy-tailed dependent risks

Let X ₁ , X ₂ denote positive heavy-tailed random variables with continuous marginal distribution functions F ₁ and F ₂, respectively. The asymptotic behavior of the tail of X ₁ +X ₂ is studied in a general copula framework and some bounds and extremal properties are provided. For more specific assumptions on F ₁ , F ₂ and the underlying dependence structure of X ₁ and X ₂, we survey explicit asymptotic results available in the literature and add several new cases.Supported by the Austrian Science Fund Project P-18392.     

Estimates from above of certain double trigonometric sums

In this paper we consider double trigonometric sums. Expressions of this type appear in some problems of quantum chaos and number theory. We are interested in rotation numbers of bounded type. We prove a uniform linear bound on double trigonometric sums along the subsequence of denominators of the continued fraction. The proof uses elementary techniques and the analysis of cancellations in sums of certain oscillatory functions over rotations. We also include a proof of a result on discrepancy for rotations of bounded type and in the Appendix we give an elementary proof of a result by Hardy and Littlewood.     

Branching random walks II

A general method is developed with which various theorems on the mean square convergence of functionals of branching random walks are proven. The results cover extensions and generalizations of classical central limit analogues as well as a result of a different type.