Mass spectrometric study of oligourea macrocycles and their anion binding behavior

Two series, one of tris‐urea macrocycles and another of hexakis‐urea macrocycles, are examined by (tandem) Fourier‐transform ion cyclotron resonance (FTICR) mass spectrometry with respect to their fragmentation patterns and anion binding properties. All macrocycles are based on two different building blocks, one of which is a very rigid xanthene unit and the other one is a more flexible diphenyl ether. The composition and the sequence of these units thus determine their flexibility. During the fragmentation of deprotonated oligourea macrocycles in the gas phase, one urea N? CO bond is cleaved followed by a scrambling reaction within the macrocycle structure. Consequently, fragments are observed that deviate from those that would be expected from the sequence of the subunits. Interesting anion binding properties involve the simultaneous recognition of two chloride anions by one of the hexakis‐urea macrocycles, whose flexibility allows this host to form a double‐helical structure. Flexibility also determines which of the hexameric receptors bears a high sulfate affinity. The interaction energy between some of the macrocycles and sulfate is high enough to even stabilize the intrinsically unstable sulfate dianion. Copyright © 2009 John Wiley & Sons, Ltd.     

Lipid domain specific recruitment of lipophilic nucleic acids: a key for switchable functionalization of membranes

Lipid domains in mammalian plasma membranes serve as platforms for specific recruitment or separation of proteins involved in various functions. Here, we have applied this natural strategy of lateral separation to functionalize lipid membranes at micrometer scale in a switchable and reversible manner. Membrane-anchored peptide nucleic acid and DNA, differing in their lipophilic moieties, partition into different lipid domains in model and biological membranes. Separation was visualized by hybridization with the respective complementary fluorescently labeled DNA strands. Upon heating, domains vanished, and both lipophilic nucleic acid structures intermixed with each other. Reformation of the lipid domains by cooling led again to separation of membrane-anchored nucleic acids. By linking appropriate structures/functions to complementary strands, this approach offers a reversible tool for triggering interactions among the structures and for the arrangement of reactions and signaling cascades on biomimetic surfaces.     

Prof. Dr. Robert Weigel elected an IEEE Fellow

SciencenewsIEEE MTT-S

Prof. Dr. Robert Weigel elected an IEEE Fellow     

Complements to ‘The Bruhat order on symmetric varieties’

We give several complements to the paper The Bruhat order on symmetric varieties. Our main result shows that the partial order on the set of twisted involutions in the Weyl groupW, which was introduced in the earlier paper, agrees with the partial order on induced by the usual Bruhat order onW.R. W. Richardson died on 15 June. 1993.     

Production and properties of polyacenaphthylene. IV: Infuence of molecular structures and end groups on the elution volumes in gel permeation chromatography

Summary Low molecular weight polyacenaphthylenes with different end groups were synthesized by cationic and free-radical initiation. The polymers were fractionated by means of GPC. Polar as well as non-polar stationary phases proved suitable for the fractionation of polyacenaphthylene. The relationship, logM=f(V_e) is within the molecular weight range (M<10⁴) non-linear and depends on the initiator used or on the type of polyreaction that occured during the polymerisation. The elution volumes of polymers prepared by thermal initiation were comparably lower than those of polymers prepared by free-radical or cationic means.This difference is not due to end group effects but can be attributed to the structure of the polymer main chain.Third communication: Thomas Stelter, Jürgen Springer, Photoabbau von Polyacenaphthylen, Makromol. Chem.185, 1719 (1984)     

Gas permeability of block copolymers of styrene and butadiene

The permeability of styrene-butadiene block copolymer foils with different composition prepared by casting and pressing has been investigated for the gases Ar, CO₂, and CH₄ at pressure difference of 400 mbar and at the temperature range 298 T [K] 333.The permeation process can be described by the solution diffusion mechanism. The diffusion coefficients decrease in the sequence of the gases Ar, CO₂, and CH₄ and the solubility coefficients increase in the sequence Ar, CH₄, CO₂.The dependence of the permeability on the composition of the block copolymer can be interpreted by the help of percolation theory and the effective medium theory. It follows the critical volume fraction of the percolation of the transport phase _PB ^c (= 0,23) and the coordination numberz (= 4) giving an information concerning the multiphase structure of the block copolymer.Presented in part at the 33^rd Annual Meeting of the Colloid-Gesellschaft, Graz, Austria, September 14–16, 1987.