Cycloaddition Reactions and Dendritic Polymer Architectures – A Perfect Match

Summery: The potential of cycloaddition (CA) reactions for the synthesis of dendritic polymers is pointed out. The [4 + 2] Diels Alder cycloaddition as well as 1,3-dipolar CA reactions including “click chemistry” are addressed, and the advantages of these reactions like high selectivity, thus high tolerance towards additional functionalities, high yields and synthesis under mild reaction conditions are highlighted. New perfectly branched dendrimers as well as hyperbranched polymers have been prepared and modified using the 1,3-dipolar cycloaddition reaction of azines with alkynes. The 1,3-dipolar CA reaction of bisazine with maleimides results in hyperbranched and thus, irregular and broadly distributed polymers though with a degree of branching of 100% due to special intermediate formation. The [4 + 2] Diels Alder cycloaddition was successfully applied for the synthesis of highly branched polyphenylene structures using the AB₂ + AB and the A₂ + B₃ approach. CA reactions are also very suitable for highly efficient polymer analogous reactions and thus, they can also be used to prepare complex polymer architectures like dendronized polymers.     

Preparation and Enantiospecific Binding of Chiral Polyelectrolyte Multilayers: An In-Situ ATR-FTIR Study

Summary: Two chiral polyelectrolyte multilayers (PEM) composed of poly(L-lysine) (PLL) and poly(vinylsulfate) (PVS) as well as poly(ethyleneimine-maltose) (PEI-m) and poly(vinylsulfate) and a nonchiral PEM composed of poly(ethyleneimine) (PEI) and poly(vinylsulfate) were deposited on a silica surface using the layer by layer method. For both PEM enantiospecific interaction towards one enantiomer of either L-/D- glutamic acid (L-/D-GLU) or L-/D-ascorbic acid (L-/D-ASC), respectively, was checked under variation of the concentration. Both deposition and enantiospecific interaction were studied by attenuated total reflection Fourier transform (ATR-FTIR) spectroscopy. Preliminary results show a significant enantiospecific preference of D- GLU over L-GLU at PEM of PLL/PVS and of D-ASC over L-ASC at PEM of PEI-m/PVS and no such preference for nonchiral PEM of PEI/PVS. PEM of PLL/PVS shows higher enantiospecifity with increasing L-/D-GLU concentration.     

Polypeptide‐Shelled Poly(propylene imine) Dendrimers and Their Complexing Properties towards Copper(II) Ions

Summary: Polypeptide‐shelled poly(propylene imine) dendrimers were realized by ring‐opening polymerization of α‐amino acid N‐carboxyanhydrides, initiated by dendrimers as core molecules. Polypeptides with 2nd generation core were used as model compounds to investigate interior complexes between metal ion and surface‐modified dendrimers. Micro‐calorimetric measurements outlined the formation of approximate 1:1 complexes between Cu^II and polypeptide‐shelled dendrimers and the influence of polypeptide chain compositions on differential molar heats of complexation.

Composition of one of the polypeptides synthesized.     

Self-pulsation and optical chaos in self-pumped photorefractive BaTiO3

Sinusoidal intensity oscillations of the phase conjugated wave reflected from a self-pumped photorefractive BaTiO₃ crystal have been observed. The oscillation amplitude is shown to be increased by providing optical feedback of the light scattered during grating formation. The oscillation frequency ? can be tuned from 0.024 Hz to 2 Hz by changing the light intensity I₀ of the object beam from 0.7 W/cm² to 100 W/cm². A power law ? ∝ I^β₀ ∝ σ with β = 0.89 was observed over this range of intensities (σ = photoconductivity). Transitions to a chaotically oscillating or a stable reflecting state have been observed at higher power levels or with increased optical feedback. An additional pump beam near the entrance face of the signal beam can decrease the build-up time for the self-pumping process by a factor of five or more.     

Ueber die Aichung der Gasuhren bei ihrer Verwendung zu chemischen Arbeiten

Ohne Zusammenfassung     

Quantum-chemical study of potassium and ammonium hexafluorozirconates

A number of fluorozirconate clusters serving as structural models for K₂ZrF₆ and (NH₄)₂ZrF₆ crystals were investigated by the Hartree-Fock ab initio method. Based on the results of quantum-chemical calculations it is shown that the differences in the structure of these compounds and in the behavior of the temperature dependence of the second moment of the ¹⁹F NMR spectra are due to differences in the binding between the cation and anion sublattices. A mechanism responsible for ionic mobility is suggested.Original Russian Text Copyright © 2004 by E. I. Voit, A. V. Voit, V. Ya. Kavun, and V. I. SergienkoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 644–650, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

On the Fourier transformation of positive,positive definite measures on commutative hypergroups,and dual convolution structures

We show that the support of the Fourier transform of a positive, positive definite measure on a commutative hypergroupK contains a positive character. This generalizes the known fact that the support of the Plancherel measure π contains a positive character (which in general is not the identity character1). It follows that contains a positive character for whenever a dual convolution exists. In particular, if1∈supp π, then1 is this character. We also give some further general results about the support of dual convolution products in terms ofsupp π. Some examples associated with Gelfand pairs and, in particular, non-compact Riemannian symmetric spaces of rank 1 are discussed.