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.

     

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     

Accreditation of reference material producers: the example of IRMM's Reference Materials Unit

The potential approaches for third-party assessment of reference material producers are revisited and the activities of the Reference Materials (RM) Unit of the Institute for Reference Materials and Measurements (IRMM) to obtain accreditation to ISO Guide 34 and ISO 17025 are described. Accreditation was related to the Unit as all matrix RM activities of the institute are concentrated there. A management system was established that allows sufficient flexibility to be applicable to a wide range of RMs while being precise enough to ensure compliance with ISO Guides 30, 31 and especially 34 and 35. Accreditation was achieved in 2004 with independent scopes for testing and RM production and was confirmed and extended in 2005. The key aspects of the RM Unit's management system for RM production are presented. Presented at BERM-10, April 2006, Charleston, SC, USA     

Development of a capillary electrophoretic method for the separation of diastereoisomers of a new human immunodeficiency virus protease inhibitor

A capillary electrophoretic (CE) method was developed for the separation of diastereoisomers of a new human immunodeficiency virus (HIV) protease inhibitor TMC114. In total 16 isomers of this drug have been synthesized (eight pairs of enantiomers). We succeeded in the separation of the eight diastereoisomers, but no enantiomers could be separated. Because of the high similarity and water-insolubility of these isomers, the separation is a real challenge. Different CE modes were tried out: capillary zone electrophoresis (CZE), nonaqueous capillary electrophoresis (NACE), micellar electrokinetic capillary chromatography (MEKC), and microemulsion electrokinetic capillary chromatography (MEEKC). Only MEEKC offered resolution of these compounds.     

Thermal Gradients for the Control of Elution in RP-LC: Application to the Separation of Model Drugs

The use of temperature as a variable in liquid chromatography enables the facile alteration of eluotropic strength without the need to change solvent composition. The ability to change eluotropic strength via temperature alone means that thermal gradients can be used to mimic the effects of solvent gradients but without many of the unwanted effects of changes in solvent composition. Here we illustrate the use of thermal gradients as a means of controlling chromatographic separations using either constant flow or, with the flow rate increased to maintain isobaric conditions, constant pressure, performed using columns packed with 1.7 μm particles. A model is described that can be used to used to predict flow, pressure and temperature under gradient conditions. Practical experimental factors such as the need for post column cooling and the use of frit restrictors in order to obtain optimum results are described.     

Infrared dichroism measurements on the alkyl chain packing of an ionic detergent intercalated between silicate layers

 Microcrystals of the metal silicate hydrate ilerite orient macroscopically on the surface of a ATR-crystals and thus, are accessible for infrared linear dichroism measurements. We present first results which indicate that the alkyl chain packing and the orientation of the polar group of dodecyltrimethylammoniumbromide (DTAB) intercalated between silicate layers can be determined in terms of infrared order parameters. The properties of DTAB can be modulated by the relative humidity of the surrounding atmosphere and by temperature. Upon heating DTAB undergoes a phase transition from a paraffin-like solid to a fluid phase. The former is characterized by the orthorhombic perpendicular packing of the frozen alkyl chains with tilted long axes. The interactions between the ionic groups of the surfactant and that of the host matrix stabilize the lamellar arrangement of DTAB in the crystalline and in the fluid phases. Received: 14 January 1998 Accepted: 27 July 1998     

Extraction of proteins from plant tissues for two-dimensional electrophoresis analysis

To increase the number of proteins detectable by two-dimensional electrophoresis (2-DE) in plants, we present a new procedure for extracting total proteins from plant tissue. This method avoids any loss of proteins in the course of sample preparation and results in two different fractions, one comprising mainly the cytoplasmatic proteins, the other one containing predominantly structure bond proteins. 2-DE patterns obtained from these two fractions show that the total number of different protein spots detected exceeds the degree of resolution commonly reported for plant proteins threefold.     

The solid-phase Nicholas reaction: scope and limitations

Two libraries of alpha-substituted alkynes has been prepared on solid phase using a sequential Sonogashira/Nicholas reaction approach. The scope of nucleophiles in the Nicholas reaction on solid phase has been investigated, including carbon, oxygen, nitrogen, sulfur, fluoride, and hydride nucleophiles. The conditions for the reaction sequence have been optimized in terms of Lewis acid, catalyst for the Sonogashira step, temperature, reaction time, and decomplexation method, enabling the five-step sequence to be performed in 1 day.