A new synthetic approach to biaryls of the rhazinilam type. Application to synthesis of three novel phenylpyridine-carbamate analogues

The synthesis of three novel racemic phenylpyridine-carbamate analogues of rhazinilam and their biological evaluation as inhibitors of microtubule assembly and disassembly by interaction with tubulin are described. The sterically hindered ortho-disubstituted biaryl unit as the challenging key structural element is first obtained by a sequential regiocontrolled nucleophilic addition of a lithium ortho-lithiohomobenzylic alkoxide species to 3-bromo-5-oxazolyl pyridine as the electrophile and a subsequent oxidation step. The incorporation of the amino group by replacement of the bromide has been achieved using a Buchwald-Hartwig amination coupling. Ultimate deprotection steps furnished free-amino and free-hydroxyl appendages which were connected by phosgenation to furnish the nine-membered median carbamate ring.     

Performance parameters for detection in low-flux coherent images

We analyze the optimization of low-flux coherent active imagery systems for target detection. We demonstrate that, unlike the Fisher ratio, the Bhattacharyya distance is an efficient figure of merit when one uses detection algorithms based on the generalized likelihood ratio test for realistic situations when the target and the background mean values are unknown. For example, we show that detection capabilities can be better if the pulse energy is divided into four shots, whereas using more than ten shots does not significantly improve the results.     

Analysis of neomycin sulfate and framycetin sulfate by high-performance liquid chromatography using evaporative light scattering detection

A rapid and simple method for the determination of main components and related substances of both neomycin sulfate and framycetin sulfate by HPLC and evaporative light scattering detection (ELSD) is described. The method was also used to determine the neomycin B and the sample sulfate content. Detection and quantitation of aminoglycoside antibiotics are problematic because of the lack of UV absorbing chromophore. The use of a universal detector avoids the need for sample derivatization or use of specific detector based on pulsed amperometry described to be difficult in routine assays. Separation was performed with a Polaris C18 150 mm x 4.6 mm i.d., 3 microm reversed-phase column with a solution of 170mM trifluoroacetic acid (TFA) mobile phase at a flow rate of 0.2 mL/min. The chromatographic parameters were optimized with the help of experimental design software. Mass spectrometry (MS) was employed to confirm the ELSD profile. The final method was validated using methodology described by the International Conference of Harmonization in the field of Active Pharmaceutical Ingredients. Commercial samples of different sources were analyzed and results were in good agreement with specifications of the European Pharmacopoeia.     

300 MHz 1H-NMR study of poly(propylene sulfide)

An ¹H 300-MHz NMR spectroscopic study of deuterated poly(propylene sulfide) shows that methylene protons are sensitive to triad effects. It was possible to distinguish i, h_i, s, and h_s triads. Experimental values found for different polymers are in good agreement with theoretical amounts obtained from statistical probability calculation. The methyl groups are also slightly stereosensitive. By using optically active deuterated monomers with different R/S ratios it was possible to confirm the assignment of peaks and the tacticity. Nondeuterated polymers give very complicated spectra, and only the highly stereoregular polymer could be analyzed through its ABCX₃ spin system.     

Regularization properties of the 2D homogeneous Boltzmann equation without cutoff

We consider the 2-dimensional spatially homogeneous Boltzmann equation for hard potentials. We assume that the initial condition is a probability measure that has some exponential moments and is not a Dirac mass. We prove some regularization properties: for a class of very hard potentials, the solution instantaneously belongs to H ^r , for some ${r\in (-1,2)}$ depending on the parameters of the equation. Our proof relies on the use of a well-suited Malliavin calculus for jump processes.     

Acoustic measures of low-frequency noise in extended high-frequency audiometry

A very high signal-to-noise ratio is required for equipment designed for extended high-frequency audiometry because listeners with almost no hearing ability in the extended high-frequency range may have normal hearing sensitivity in the lower frequencies. Two commercially available systems designed for pure-tone audiometry were evaluated both in the conventional and extended high-frequency range. Unwanted lower frequency signals greater than the noise floor occurred predominantly at presentation levels of approximately 110 dB SPL or higher. Test tones in the extended high-frequency range should be restricted to levels that are not associated with lower frequency noise.