Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M4L6 Cobalt and Nickel Cages

Subtle differences in metal–ligand bond lengths between a series of [M₄L₆]^4? tetrahedral cages, where M=Fe^II, Co^II, or Ni^II, were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single‐crystal X‐ray diffraction was used to study the solid‐state complexes of the iron(II) and nickel(II) cages.     

Nelumbo nucifera leaves as source of water-repellent wax: Extraction through polar and non-polar organic solvents

Nelumbo nucifera leaves are rich source of natural wax possessing super-hydrophobic properties. It provides protection to them from ecological turbulences and climatic wear and tear. In this study, various experiments have been conducted to observe the yield of extraction and the determination of various functional groups, which are present in natural wax, derived from Nelumbo nucifera leaves. The natural wax has been extracted from lotus leaves through non-polar (hexane) and polar (ethanol) solvent via different extraction methods. The superhydrophobic wax has been successfully extracted with hexane. Whereas, ethanol did not extract the water-repellent wax of lotus leaf. Considering the cumulative amount, i.e. (desired + undesired), the maceration shows the extraction of 2.9% (%w/w, through hexane) and 10.2% (%w/w, through ethanol), while it was found 2.5% (%w/w, cycle period 15 min) and 9.0% (%w/w, cycle period 26 min) respectively, in case of Soxhlet extraction technique. For this specific case of natural wax recovery from biomass (lotus leaf), the maceration (traditional method) resulted a little bit superior extraction yield in comparison to the Soxhlet extraction method for extraction of crude wax. In the case of non-polar solvent (hexane), an extraction yield of 1.97% (%w/w) through maceration method was observed while in the case of non-polar solvent (ethanol), an extraction yield of 1.62% (%w/w) through Soxhlet extraction was observed. The TLC analysis on both types of extracts was performed. For the detection of various hydrocarbon chains in the crude wax extracts, FTIR was also performed. Topography of wax surface and wax-coated waterproof fabric was compared through SEM.     

Aromatic Superhalogens

No organic molecules with electron affinities near or above those of halogens are known. We show for the first time that aromaticity rules can be used to design molecules with electron affinities far exceeding those of halogen atoms either by tailoring the ligands of cyclopentadienyl or by multiple benzoannulations of cyclopentadienyl in conjunction with the substitution of CH groups with isoelectronic N atoms. Results based on density functional theory revealed that the electron affinities of some of these organic molecules can reach as high as 5.59 eV, thus opening the door to new class of superhalogens that contain neither a metal nor a halogen atom.     

Nickel‐Catalyzed α‐Carbonylalkylarylation of Vinylarenes: Expedient Access to γ,γ‐Diarylcarbonyl and Aryltetralone Derivatives

We report a Ni‐catalyzed regioselective α‐carbonylalkylarylation of vinylarenes with α‐halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary, and tertiary α‐halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates γ,γ‐diarylcarbonyl derivatives with α‐secondary, tertiary, and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug.     

Alteration in Cross Diffusivities Governs the Nature and Dynamics of Spatiotemporal Pattern Formation

Realizing spatiotemporal patterns out of a chemical reaction diffusion system remains an experimental challenge owing to the difficulty in overcoming the stringent condition of diffusion driven instability. Herein, by considering the spatially extended Gray-Scott model system, we have investigated how the cross diffusivities of the reactants involved influence the nature and dynamics of spatiotemporal patterns. Our study unravels that in absence of diffusion driven instability, spatially inhomogeneous patterns can be obtained for the Gray-Scott model system, and unstable time dependent patterns can be stabilized just by adjusting cross diffusivities of the reactants. Interestingly, the effect of cross diffusion in presence of the diffusion driven instability can differentially alter the speed of pattern formation, and potentially modify the nature of the spatiotemporal patterns obtained under different parametric conditions. Experimental verification of our findings may allow us to observe spatiotemporal patterns beyond the regime of classical Turing instability.     

Antibacterial Activity of Alpinia galanga (L) Willd Crude Extracts

Methanol, acetone and diethyl ether extracts of Alpinia galanga have been evaluated against pathogens viz. Bacillus subtilis MTCC 2391, Enterobacter aerogene, Enterobacter cloacae, Enterococcus faecalis, Escherichia coli MTCC 1563, Klebsiella pneumoniae, Pseudomonas aeruginosa MTCC 6642, Salmonella typhimurium, Staphylococcus aureus and Streptococcus epidermis using Agar well diffusion method. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of all the extracts were determined using the macrodilution method. Methanol extracts have shown excellent activity towards all the pathogens with MIC and MBC values ranging from 0.04–1.28 mg/ml and 0.08–2.56 mg/ml, respectively. The GC–MS analysis of methanol extracts have yielded compounds like 5-hydroxymethyl furfural (59.9%), benzyl alcohol (57.6%), 1,8 cineole (15.65%), methylcinnamate (9.4%), 3-phenyl-2-butanone (8.5%) and 1,2 benzenedicarboxylic acid (8.9%), which could be responsible for its broad spectrum activity. So, A. galanga can be quite resourceful for the development of new generation drugs.     

Catalyst electronic polarizability and enantiomeric excess in asymmetric hydrogenation

In the classical rhodium-diphosphine complexes-catalyzed asymmetric hydrogenation of enamide substrates, examination on the role of catalyst electronic polarizability in the origin of enantioselectivity reveals its linear free energy relationship with the product enantiomeric ratio that is much more pronounced than analogous correlation with steric effect in the same systems. From a conceptually novel scenario, this work suggests that the often-overlooked chiral catalyst local polarizability property may function as a controlling force in enantioselection thus has important implication in rational catalyst design.     

Enhanced podophyllotoxin production from Agrobacterium rhizogenes transformed cultures of Podophyllum hexandrum

Podophyllotoxin, a potent chemotherapeutic agent is obtained from Podophyllum hexandrum Royle. Embryos of P. hexandrum were transformed using different strains of Agrobacterium rhizogenes viz. A4, 15834, K599. Transformed nature of the calli was ascertained and the cultures were further maintained as individual clones. HPLG analysis of transformed cultures depicted a three-fold increase in podophyllotoxin content in comparison to controls.     

Exchange bias with Fe substitution in LaMnO<Subscript>3</Subscript>

We observe the negative shift of the magnetic hysteresis loop at 5 K, while the sample is cooled in external magnetic field in case of 30% of Fe substitution in LaMnO₃. The negative shift and training effect of the hysteresis loops indicate the phenomenon of exchange bias. The cooling field dependence of the negative shift increases with the cooling field below 7.0 kOe and then, decreases with further increase of cooling field. The temperature dependence of the negative shift of the hysteresis loops exhibits that the negative shift decreases sharply with increasing temperature and vanishes above 20 K. Temperature dependence of dc magnetization and ac susceptibility measurements show a sharp peak (T_p) at 51 K and a shoulder (T_f) around 20 K. The relaxation of magnetization shows the ferromagnetic and glassy magnetic components in the relaxation process, which is in consistent with the cluster-glass compound.     

Development and validation of a highly sensitive LC‐MS/MS‐ESI method for the determination of bicalutamide in mouse plasma: application to a pharmacokinetic study

A highly sensitive, rapid assay method has been developed and validated for the estimation of bicalutamide in mouse plasma using liquid chromatography coupled to tandem mass spectrometry with electrospray ionization in the negative‐ion mode. The assay procedure involves extraction of bicalutamide and tolbutamide (internal standard, IS) from mouse plasma with a simple protein precipitation method. Chromatographic separation was achieved using an isocratic mobile phase (0.2% formic acid:acetonitrile, 35:65, v/v) at a flow rate of 0.5 mL/min on an Atlantis dC₁₈ column (maintained at 40 ± 1°C) with a total run time of 3.0 min. The MS/MS ion transitions monitored were m/z 428.9 → 254.7 for bicalutamide and m/z 269.0 → 169.6 for IS. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. The lower limit of quantitation achieved was 1.04 ng/mL and the linearity range extended from 1.04 to 1877 ng/mL. The intra‐ and inter‐day precisions were in the ranges of 0.49–4.68 and 2.62–4.15, respectively. Copyright © 2012 John Wiley & Sons, Ltd.