Phase behavior at low temperature of poly(tetrafluoroethylene) by temperature-modulated calorimetry

Temperature modulated differential calorimetry (TMDSC) is used to examine the crystal-crystal transitions of poly(tetrafluoroethylene). This study gives new information about the dynamic thermal behavior of such transitions. The involvement of reversible and irreversible processes during the phenomenon is observed, which are related to the order-disorder changes occurring during the transition.This study adds a new example to the response of TMDSC during first order transitions.     

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.     

New HPLC-chiral stationary phases for enantiomeric resolution of sulfoxides and selenoxides

Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB) containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical separations to a semi-preparative and preparative scale.     

Quantitative Concentration Inequalities for Empirical Measures on Non-compact Spaces

We establish quantitative concentration estimates for the empirical measure of many independent variables, in transportation distances. As an application, we provide some error bounds for particle simulations in a model mean field problem. The tools include coupling arguments, as well as regularity and moment estimates for solutions of certain diffusive partial differential equations.     

Calorimetric and diffractometric study of the lowest room-temperature transition of polytetrafluoroethylene

Through differential scanning calorimetry and wide angle x-ray scattering, the room-temperature transitions of native (never melted) polytetrafluoroethylene have been investigated. The independence of the transitions, and in particular of the lowest one, on the heating kinetics, seems to suggest that also this transition is a true crystal-crystal transition.     

Boundary and Lens Rigidity of Lorentzian Surfaces

Let be a Lorentzian metric on the plane that agrees with the standard metric outside a compact set and so that there are no conjugate points along any time-like geodesic of . Then and are isometric. Further, if and are two dimensional compact time oriented Lorentzian manifolds with space--like boundaries and so that all time-like geodesics of maximize the distances between their points and and are ``boundary isometric', then there is a conformal diffeomorphism between and and they have the same areas. Similar results hold in higher dimensions under an extra assumption on the volumes of the manifolds.

     

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.     

A Synthesis of imidazo- and pyrimido[1,2-g][1,6]naphthyridinones

Arylmethylimidazolines and (3-chlorophenyl)methyl-1,4,5,6-tetrahydropyrimidine amidated 2-chloro-3-pyridinecarbonyl chloride, and potassium t-butoxide cyclized the products to linearly fused, tricyclic imidazo-and pyrimido[1,2-g][1,6]naphthyridinones. Condensation of ethyl 2-chloro-3-pyridinecarboxylate with 2-(phenylmethyl)imidazoline in the presence of sodium methoxide directly formed the isomeric, angularly fused 8,9-dihydro-6-phenylimidazo[1,2-a ] [1,8]naphthyridin-5(7H-one.     

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.