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. 相似文献
We present susceptibility, microwave resistivity, NMR and heat-capacity results for Li1-xZnx(V1-yTiy)2O4 with 0 ?x? 0.3 and 0 ?y? 0.3. For all doping levels the susceptibility curves can be fitted with a Curie-Weiss law. The paramagnetic Curie-Weiss temperatures
remain negative with an average value close to that of the pure compound Θ≈ - 36 K. Spin-glass anomalies are observed in the susceptibility, heat-capacity and NMR measurements for both type of dopants.
From the temperature dependence of the spin-lattice relaxation rate we found critical-dynamic behavior in the Zn doped compounds
at the freezing temperatures. For the Ti-doped samples two successive freezing transitions into disordered low-temperature
states can be detected. The temperature dependence of the heat capacity for Zn-doped compounds does not resemble that of canonical
spin glasses and only a small fraction of the total vanadium entropy is frozen at the spin-glass transitions. For pure LiV2O4 the spin-glass transition is completely suppressed. The temperature dependence of the heat capacity for LiV2O4 can be described using a nuclear Schottky contribution and the non-Fermi liquid model, appropriate for a system close to
a spin-glass quantum critical point. Finally an (x/y, T)-phase diagram for the low-doping regime is presented.
Received 16 March 2001 and Received in final form 30 October 2001 相似文献
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.
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 相似文献
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. 相似文献
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. 相似文献
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. 相似文献