Fast Si magic-angle-spinning NMR acquisitions by RAPT-CP Al → Si polarization transfer

Using enhancement of the ²⁷Al central-transition magnetization by applying RAPT prior to ²⁷Al → ²⁹Si cross-polarization, we demonstrate fast acquisition of ²⁹Si one-dimensional MAS and two-dimensional ²⁷Al–²⁹Si HETCOR spectra on a new sialon phase Ba₂Al₃Si₉N₁₃O₅.     

The diastereoselective synthesis of functionalised isoxazolidines using a Cope elimination/intramolecular nitrone cycloaddition strategy

Functionalised hydroxylamine derivatives of (S)-prolinol prepared by a Cope elimination have been found to undergo oxidation to the nitrone either in the presence of air or a catalytic quantity of TPAP. These undergo intramolecular cycloaddition to give tricyclic isoxazolidines with high diastereoselectivity.     

The synthesis of chiral functionalised morpholine N-oxides using a tandem Cope elimination/reverse-Cope elimination protocol

Hydroxylamine derivatives of (S)-prolinol have been generated using a Cope elimination. These undergo reverse-Cope elimination onto a pendant double bond to give morpholine N-oxides containing three contiguous chiral centres.     

Molecular gradients: an efficient approach for optimizing the surface properties of biomaterials and biochips

A variety of molecular gradients of alkanethiols with the structure HS-(CH(2))(m)-X (m = 15; X = COOH, CH(2)NH(2), or CH(3)) and oligo(ethylene glycol)-terminated alkanethiols with the structures HS-(CH(2))(15)-CO-NH-Eg(n) (n = 2, 4, or 6), HS-(CH(2))(15)-CO-NH-Eg(2)-(CH(2))(2)-NH-CO-(CH(2))(4)-biotin, and HS-(CH(2))(15)-CO-NH-Eg(6)-CH(2)-COOH were prepared on polycrystalline gold films. These gradients were designed to serve as model surfaces for fundamental studies of protein adsorption and immobilization phenomena. Ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopy, operating in scanning mode, were used to monitor the layer composition, gradient profiles, tail group conformation, and overall structural quality of the gradient assemblies. The gradient profiles were found to be 4-10 mm wide, and they increased in width with increasing difference in molecular complexity between the thiols used to form the gradient. The oligo(ethylene glycol) thiols are particularly interesting because they can be used to prepare so-called conformational gradients, that is, gradients that display a variation in oligo(ethylene glycol) chain conformation from all trans on the extreme Eg(2,4) sides, via an amorphous-like phase in the mixing regimes, to helical at the extreme Eg(6) sides. We demonstrate herein a series of experiments where the above gradients are used to evaluate nonspecific binding of the plasma protein fibrinogen, and in agreement with previous studies, the highest amounts of nonspecifically bound fibrinogen were observed on all-trans monolayers, that is, on the extreme Eg(2,4) sides. Moreover, gradients between Eg(2) and a biotinylated analogue have been prepared to optimize the conditions for the immobilization of streptavidin. Ellipsometry and infrared spectroscopy reveal high levels of immobilization over a fairly broad range of compositions in the gradient regime, with a maximum between 50 and 60% of the biotinylated analogue in the monolayer. A pI gradient composed of (NH(3)(+)/COO(-))-terminated thiols was also prepared and evaluated with respect to its ability to separate differently charged proteins, pepsin, and lysozyme, on a solid surface.     

Nuclear Fréchet spaces without bases III. Every nuclear Fréchet space not isomorphic to ω admits a subspace and a quotient space without a strong finite dimensional decomposition

The result stated in the title is proved.Research of the second author partially supported by the National Science Foundation. He would also like to thank the Banach Institute, Polish Academy of Sciences and Universität Kaiserslautern for their hospitality.     

Expedient synthesis of novel β-ketoesters from the Mizoroki–Heck coupling of ethyl 3-ethoxyacrylate with aryl and pyridyl halides

It is well known that β-ketoesters are useful intermediates for the synthesis of a range of heterocyclic templates. While there are many useful synthetic methods available to access these intermediates, there are still opportunities for the discovery of useful methodologies for their construction from novel starting materials. In this regard, we report on the discovery of a facile Pd-catalyzed Mizoroki–Heck coupling of ethyl 3-ethoxyacrylate with aryl and heteroaryl halides to form substituted alkoxyacrylates which can be hydrolyzed to form novel aryl and heteroaryl β-ketoesters.     

Liquid Chromatographic Analysis of Various Formulations Containing Emtricitabine

A gradient liquid chromatographic (LC) method for control of emtricitabine (FTC) was validated for the analysis of FTC formulations (capsules and oral solution) and fixed-dose-combination tablets containing FTC [FTC combined with tenofovir disoproxil fumarate (TDF) and FTC combined with TDF and efavirenz (EFV)]. The method is based on the purity test recently prescribed in the International Pharmacopoeia and uses a Hypersil BDS C18 column (25 cm × 4.6 mm i.d.), 5 μm kept at a temperature of 35 °C. Other reversed-phase columns were also investigated. The mobile phases for gradient elution consist of acetonitrile, phosphate buffer and water. The flow rate is 1.0 mL min⁻¹ and UV detection is performed at 280 nm. The method is capable of separating the main components from one another, from the inactive ingredients and from the main degradation products. The method was validated with respect to accuracy, precision, sensitivity and linearity for each component and the solution media were optimized. Finally, commercial FTC capsules, FTC oral solution, FTC/TDF tablets and FTC/TDF/EFV tablets were examined.