Functionalized poly(oxanorbornene)‐block‐copolymers: Preparation via ROMP/click‐methodology

Block copolymers on basis of poly(oxanorbornenes) bearing functional moieties in their side‐chains are prepared via a combination of ROMP‐methods and 1,3‐dipolar‐“click”‐reactions. Starting from N‐substituted‐ω‐bromoalkyl‐oxanorbornenes and alkyl‐/perfluoroalkyl‐oxanorbornenes, block copolymers with molecular weights up to 25,000 g mol^?1 were generated. Subsequent nucleophilic exchange‐reactions yielded the block‐copolymers functionalized with ω‐azidoalkyl‐moieties in one block. The 1,3‐azide/alkine‐“click” reactions with a variety of terminal alkynes in the presence of a catalyst system consisting of tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1‐benzyl‐5‐methyl‐1H‐ [1,2,3]triazol‐4‐ylmethyl)‐amine furnished the substituted block copolymers in high yields, as proven by NMR‐spectroscopy. The resulting polymers were investigated via temperature‐dependent SAXS‐methods, revealing their microphase separated structure as well as their temperature‐dependent behavior. The presented method offers the generation of a large set of different block‐copolymers from only a small set of starting materials because of the high versatility of the “click” reaction, thus enabling a simple and complete functionalization after the initial polymerization reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 485–499, 2007     

Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Metal-Assisted Oxidative Cyclization of Arylamidrazones I. Synthesis of 3-Acetyl-1,4-dihydro-1-phenyl-1,2,4-benzotriazine

In the presence of RuCl₃, N-phenylamidrazone underwent oxidative cyclization into 1,4-dihydro-1-phenyl-1,2,4-benzotriazine, the structure of which is established by spectral and X-ray diffraction data.     

Synthesis of Surface-Modified Nanoparticles via Cycloaddition-Reactions

Summary. The surface modification of nanoparticles via azide/alkine-1,3-dipolar cycloaddition-reactions is described. Ligand exchange onto various nanoparticles was monitored by ¹H NMR spectroscopy and formed the basis for the attachment of ligands onto the nanoparticles and their subsequent modification by dipolar cycloaddition reactions. Nanoparticle-surfaces were monitored by binding onto self-assembled monolayers derivatized with matching supramolecular interactions after derivatization.     

Algebraic properties of discrete box splines

The central objective of this paper is to discuss linear independence of translates of discrete box splines which we introduced earlier as a device for the fast computation of multivariate splines. The results obtained here allow us to draw conclusions about the structure of such discrete splines which have, in particular, applications to counting the number of nonnegative integer solutions of linear diophantine equations.     

A characterization of the \Sigma_1-definable functions of KP\omega + (uniform\; AC)

The subject of this paper is a characterization of the -definable set functions of Kripke-Platek set theory with infinity and a uniform version of axiom of choice: . This class of functions is shown to coincide with the collection of set functionals of type 1 primitive recursive in a given choice functional and . This goal is achieved by a G?del Dialectica-style functional interpretation of and a computability proof for the involved functionals. Received October 9, 1996     

Two Ergodic Sample-Path Properties of the Poisson Process

For increasing sequences of real numbers we consider two types of asymptotic behavior that remind of the defining property of a (homogeneous) Poisson process according to which the numbers of points in disjoint intervals are independent and follow Poisson distributions with specified parameters. We prove that almost all paths of a Poisson process show this asymptotic behavior, and characterize the Poisson process by these properties. Further we discuss the connection to equidistribution notions.