Synthesis and NMR assignment of pentacycloundecane precursors of potential pharmaceutical agents

The synthesis and complete NMR elucidation of eight novel pentacycloundecane (PCU) derivatives are reported. These compounds are precursors in the synthesis of PCU‐based anti‐tuberculosis (TB) agents and potential human immunodeficiency virus (HIV) protease inhibitors. Two‐dimensional (2D) NMR techniques were used to assign the NMR spectra for these compounds. Substitution of the cage molecule at (C‐8/11) further complicates the assignment, since some of the substituted alkyl chain groups overlap with the cage proton signals. The side chain heteroatoms also introduce a rare through‐space deshielding effect to some of the carbon atoms of the cage skeleton. Ring strain in the rigid cage skeleton appears to induce drastic electronic changes in some parts of the cage framework. This observation is more dramatic for the C‐4 methylene group of the cage diols and the cage ethers. Copyright © 2010 John Wiley & Sons, Ltd.     

Coriolis Effect on the Linear Stability of Convection in a Porous Layer Placed Far Away from the Axis of Rotation

The linear stability theory is used to investigate analytically the Coriolis effect on centrifugally driven convection in a rotating porous layer. The problem corresponding to a layer placed far away from the axis of rotation was identified as a distinct case and therefore justifying special attention. The stability of the basic centrifugally driven convection is analysed. The marginal stability criterion is established as a characteristic centrifugal Rayleigh number in terms of the wavenumber and the Taylor number.     

Stability of Convection in a Gravity Modulated Porous Layer Heated from Below

The linear stability theory is used to investigate analytically the effects of gravity modulation on convection in a homogenous porous layer heated from below. The gravitational field consists of a constant part and a sinusoidally varying part, which is tantamount to a vertically oscillating porous layer subjected to constant gravity. The linear stability results are presented for the specific case of low amplitude vibration for which it is shown that increasing the frequency of vibration stabilises the convection.     

Weak Nonlinear Analysis of Moderate Stefan Number Oscillatory Convection in Rotating Mushy Layers

We consider the solidification of a binary alloy in a mushy layer subject to Coriolis effects. A near-eutectic approximation and large far-field temperature is employed in order to study the dynamics of the mushy layer with a Stefan number of unit order of magnitude. The weak nonlinear theory is used to investigate analytically the Coriolis effect in a rotating mushy layer for a new moderate time scale proposed by the author. It is found that increasing the Taylor number favoured the forward bifurcation.     

Antiproliferative activity of chelating N,O- and N,N-ruthenium(II) arene functionalised poly(propyleneimine) dendrimer scaffolds

Chelating neutral (N,O) and cationic (N,N) first- and second-generation ruthenium(II) arene metallodendrimers based on poly(propyleneimine) dendrimer scaffolds were obtained from dinuclear arene ruthenium precursors by reactions with salicylaldimine and iminopyridyl dendritic ligands, respectively. The N,N cationic complexes were isolated as hexafluorophosphate salts and were characterised by NMR and IR spectroscopy, and MALDI-TOF mass spectrometry. Related mononuclear complexes were obtained in a similar manner and their molecular structures have been determined by X-ray diffraction analysis. The cytotoxicities of the mono- and multinuclear complexes were established using A2780 and A2780cisR human ovarian carcinoma cancer cell lines.     

NMR elucidation of a novel (S)-pentacyclo-undecane bis-(4-phenyloxazoline) ligand and related derivatives

The NMR elucidation of a novel ligand (S)-pentacyclo-undecane bis-(4-phenyloxazoline) and related pentacyclo-undecane (PCU) derivatives is reported. Two-dimensional NMR proved to be a powerful technique in overcoming the difficulties associated with the elucidation of these compounds when only one-dimensional NMR data is utilized. A chiral substituent was introduced to both 'arms' of the PCU skeleton to produce derivatives 1-3. These derivatives display C(1) symmetry with all thecage atoms being nonequivalent. Owing to overlapping of peaks in the (1)H spectra, identification of these diastereomeric protons was very difficult. The (13)C spectra gave rise to clear splitting of the nonequivalent carbons. This is unusual compared to similar PCU derivatives with chiral substituents as splitting of all the diastereomeric cage carbons has not yet been reported. Nuclear Overhauser enhancement spectroscopy (NOESY) correlations of derivatives 1-3 confirm the different conformations of the molecule in which the side 'arms' occupy different orientations with respect to cage moiety.     

Chitosan–sodium alginate encapsulated Co-doped ZrO<Subscript>2</Subscript>–MWCNTs nanocomposites for photocatalytic decolorization of organic dyes

Photocatalytic decolorization properties of cobalt doped-ZrO₂-multiwalled carbon nanotubes (Co–ZrO₂–MWCNTs) and chitosan–sodium alginate encapsulated Co–ZrO₂–MWCNTs (CS/Alg–Co–ZrO₂–MWCNTs) with varying weight percentage of Co–ZrO₂–MWCNTs are presented in this research paper. The Co–ZrO₂–MWCNTs was first synthesized through homogenous co-precipitation method and introduced into the chitosan–sodium sodium alginate (CS/Alg) biopolymer matrix. The bio-nanocomposites were characterized using X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, (UV–Vis)-spectroscopy and energy dispersive spectroscopy to obtain information on their structure, formation, morphology, size and elemental analysis. The photodecolorization efficiency of the samples was determined through their decolorization of trypan blue dye aqueous solution in 180 min. Recyclability of the catalysts was also assessed. The bio-nanocomposites experienced reduced band gap values with subsequent improvement in visible light activity compared to the uncapped Co–ZrO₂–MWCNTs. All the CS/Alg–Co–ZrO₂–MWCNTs exhibited higher photodecolorization activities than the uncapped Co–ZrO₂–MWCNTs. The most efficient catalyst (CS/Alg–40 % Co–ZrO₂–MWCNTs) with a band gap of 2.56 eV displayed 94 % decolorization efficiency of the dye. Though reusability of the catalyst is significant, its efficiency diminished consistently after each cycle.     

The structure of ion-acoustic waves in a low-frequency three-component electron–ion space plasma with two-electron populations

In the present paper, we have studied the binding energy of the shallow donor hydrogenic impurity, which is confined in an inhomogeneous cylindrical quantum dot (CQD) of \(\hbox {GaAs-Al}_{x}\hbox {Ga}_{1-x}\hbox {As}\). Perturbation method is used to calculate the binding energy within the framework of effective mass approximation and taking into account the effect of dielectric mismatch between the dot and the barrier material. The ground-state binding energy of the donor is computed as a function of dot size for finite confinement. The result shows that the ground-state binding energy decreases with the increase in dot size. The result is compared with infinite dielectric mismatch as a limiting case. The binding energy of the hydrogenic impurity is maximum for an on-axis donor impurity.     

Chiral hetero- and carbocyclic compounds from the asymmetric hydrogenation of cyclic alkenes

Several types of chiral hetero- and carbocyclic compounds have been synthesized by using the asymmetric hydrogenation of cyclic alkenes. N,P-Ligated iridium catalysts reduced six-membered cyclic alkenes with various substituents and heterofunctionality in good to excellent enantioselectivity, whereas the reduction of five-membered cyclic alkenes was generally less selective, giving modest enantiomeric excesses. The stereoselectivity of the hydrogenation depended more strongly on the substrate structure for the five- rather than the six-membered cyclic alkenes. The major enantiomer formed in the reduction of six-membered alkenes could be predicted from a selectivity model and isomeric alkenes had complementary enantioselectivity, giving opposite optical isomers upon hydrogenation. The utility of the reaction was demonstrated by using it as a key step in the preparation of chiral 1,3-cis-cyclohexane carboxylates.