Synthesis,and Antimycobacterial and Cytotoxic Evaluation of Certain Fluoroquinolone Derivatives

Certain 1‐ethyl‐ and 1‐aryl‐6‐fluoro‐1,4‐dihydroquinol‐4‐one derivatives were synthesized and evaluated for antimycobacterial and cytotoxic activities. Preliminary results indicated that, for 1‐aryl‐6‐fluoroquinolones, both 7‐(piperazin‐1‐yl)‐ and 7‐(4‐methylpiperazin‐1‐yl) derivatives, 9b and 11a , are able to completely inhibit the growth of M. tuberculosis at a concentration of 6.25 μg/ml, while the 7‐[4‐(2‐oxo‐2‐phenylethyl)piperazin‐1‐yl] derivative 13 exhibits only 31% growth inhibition at the same concentration. For 1‐ethyl‐6‐fluoroquinolones, both 7‐[4‐(2‐oxopropyl)piperazin‐1‐yl]‐ and 7‐[4‐(2‐oxo‐2‐phenylethyl)piperazin‐1‐yl]‐derivatives, 2a and 2b , respectively, show complete inhibition, while their 2‐iminoethyl and substituted phenyl counterparts 3a and 2c are less active. In addition, the 6,8‐difluoro derivative was a more‐favorable inhibitor than its 6‐fluoro counterpart ( 2b vs. 2d ). These results deserve full attention especially because 2a, 2b, 9b , and 11a are non‐cytotoxic at a concentration of 100 μM . Furthermore, compound 9b proved to be a potent anti‐TB agent with selective index (SI)>40 and an EC₉₀ value of 5.75 μg/ml.     

Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties

N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine was synthesized from N‐(4‐nitrophenyl)‐diphenylamine by the Vilsmeier‐Haack reaction. Soluble aromatic poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine and aromatic diamine in N‐methyl‐2‐pyrrolidone (NMP) at room temperature under reduced pressure. All the PAMs are highly soluble in various organic solvents, such as N,N‐dimethylacetamide (DMAc), chloroform (CHCl₃), and tetrahydrofuran (THF). Differential scanning calorimetry (DSC) indicated that these PAMs had glass‐transition temperatures (T_gs) in the range of 170–230 °C, and a 10% weight‐loss temperatures in excess of 490 °C with char yield at 800 °C in nitrogen higher than 60%. These PAMs in NMP solution showed UV‐Vis charge‐transfer (CT) absorption at 405–421 nm and photoluminescence peaks around 462–466 nm with fluorescence quantum efficiency (Φ_F) 0.10–0.99%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4921–4932, 2007     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

Bounds for non‐periodic mixtures of infinitely many materials

We prove bounds on the homogenized coefficients for general non‐periodic mixtures of an arbitrary number of isotropic materials, in the heat conduction framework. The component materials and their proportions are given through the Young measure associated to the sequence of coefficient functions. Upper and lower bounds inequalities are deduced in terms of algebraic relations between this Young measure and the eigenvalues of the H‐limit matrix. The proofs employ arguments of compensated compactness and fine properties of Young measures. When restricted to the periodic case, we recover known bounds. Copyright © 2005 John Wiley & Sons, Ltd.     

Barium(II)–2,4‐dinitrophenolate–18‐crown‐6 at 183 K

The title compound, bis(2,4‐dinitrophenolato‐κ²O,O′)(1,4,7,10,13,16‐hexaoxadecane‐κ⁶O)barium(II), [Ba(C₆H₃N₂O₅)₂(C₁₂H₂₄O₆)], is a 1:1 complex of barium(II)–2,4‐di­nitro­phenolate and 1,4,7,10,13,16‐hexaoxa­cyclo­octa­decane (18‐crown‐6). Its structure is located on a crystallographic inversion centre. The temperature dependence of the crystal structure has been studied. The monoclinic β angle of the P2₁/­n space group increases with increasing temperature. The packing structure of the complex is stabilized by intermolecular C—H?O interactions.     

Intramolecular motion and isotope effects in muonium‐substituted chloroalkyl radicals

Muon irradiation of pure liquid 3‐chloropropene, CH₂=CH-CH₂Cl, yields a primary radical, \dot\mboxCH₂-CHMu-CH₂Cl, and a secondary radical, MuCH₂-\rm\dot\mboxCH-CH₂Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH₂-\rm\dot\mboxC(CH₃)-CH₂Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH₃,-CH₂Cl and -CH₂Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H. This revised version was published online in August 2006 with corrections to the Cover Date.