Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

Development of a novel approach for the production of dried genomic DNA for use as standards for qualitative PCR testing of food-borne pathogens

As part of a multi-centre European project, FOOD-PCR, the feasibility of a novel approach for production of dried bacterial DNA that could be used as certified reference materials (CRM) was assessed. Selected strains of Salmonella typhimurium, Listeria monocytogenes, Escherichia coli O157, Campylobacter jejuni and Yersinia enterocolitica were used to produce genomic DNA (gDNA). These preparations gave support to method development for qualitative polymerase chain reaction (PCR) detection methods for food-borne pathogens. Purified gDNA was transformed into stable and dry gDNA by using polypropylene vials as carrier and applying a vacuum-drying technique. The gDNA preparations were shown to be sufficiently stable under ambient transport conditions without cooling and proved to have long-term stability at 5°C of at least 22 months. The dried DNA was easily reconstituted by addition of distilled water then gentle shaking. These studies have shown that production of stable and dry bacterial gDNA material is feasible and could help satisfy the increasing need for certified reference DNA positive control samples in the field of PCR testing for detection and verification of food-borne microbial pathogens.

     

Discovery of a new long-lived isomeric state in 125Ce

A new long-lived isomeric state in the near proton dripline nucleus ¹²⁵Ce has been identified with Schottky mass spectrometry at GSI. The excitation energy E ^* = 103(12)keV and the decay time of 193(1)s have been obtained from a single stored fully ionized ^125m Ce⁵⁸⁺ ion. The data implies an E3 transition and a 1/2⁺ assignment for the spin of the isomer.     

Direct mass measurements of neutron-deficient 152Sm projectile fragments at the FRS-ESR facility

The FRS-ESR facility at GSI provides one of the most efficient methods for direct mass measurements. In the present experiment, exotic nuclei were produced via fragmentation of ¹⁵²Sm projectiles in a thick beryllium target at 500-600 MeV/u, separated in-flight with the fragment separator FRS, and injected into the storage-cooler ring ESR. Time-resolved Schottky Mass Spectrometry was applied for mass measurements of stored and electron-cooled bare and few-electron ions. 373 different nuclides were identified by means of the spectra of their revolution frequencies. Masses for 18 nuclides (⁸⁴Zr, ⁹²Ru, ⁹⁴Rh, ^107,108,110Sb, ^111,112,114I, ¹¹⁸Ba, ^122,123La, ¹²⁴Ce, ¹²⁷Pr, ¹²⁹Nd, ¹³²Pm, ¹³⁴Sm, ¹³⁷Eu) have been determined for the first time. Masses for ^111,112I and ¹¹³Xe have been obtained via known α-decay energies. The experiment and first results will be presented.     

Isobar separation at FRS-ESR – a development towards pure isomeric stored beams

One important goal of the ILIMA project at FAIR is the study of masses and decay properties of relativistic isomeric beams stored and cooled in the planned storage-ring complex. A new scheme is described, where a storage-cooler ring is used for high-resolution mass separation. Experimental results on the separation of the isobaric pair ¹⁴⁰Pr-¹⁴⁰Ce are presented. P. Beller, deceased.     

Depth profiling of latex blends of fluorinated and fluorine‐free acrylates with laser‐induced secondary mass spectrometry

We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003     

Level Density of the Hénon-Heiles System Above the Critical Barrier Energy

We discuss the coarse-grained level density of the Hénon-Heiles system above the barrier energy, where the system is nearly chaotic. We use periodic orbit theory to approximate its oscillating part semiclassically via Gutzwiller’s semiclassical trace formula (extended by uniform approximations for the contributions of bifurcating orbits). Including only a few stable and unstable orbits, we reproduce the quantum-mechanical density of states very accurately. We also present a perturbative calculation of the stabilities of two infinite series of orbits (R_n and L_m), emanating from the shortest librating straight-line orbit (A) in a bifurcation cascade just below the barrier, which at the barrier have two common asymptotic Lyapunov exponents χ_R and χ_L.     

Sphere orders

Ann-sphere order is a finite partially ordered set representable by containment ofn-spheres in Euclidean (n+1)-space. We present a sequence {P _i } of ordered sets such that eachP _i is ann-sphere order only forni; one consequence is that we are able to determine the dimension of a Euclidean space-time manifold from the finite suborders of its causality order.Research supported by ONR grant N00014 85-K-0769.