Metathesis polymerization of N-aryl norbornene dicarboximides. I

Metathesis polymerization of N-phenyl-exo-norbornene dicarboximide and ortho/meta/para methyl substituted phenyl nadimides was carried out using WCl₆/tetramethyltin. Structural characterization was done by FTIR, ¹H- and ¹³C-NMR. A mixture of cis and trans double bond structures were introduced in the backbone during polymerization. The cis content was higher (52 to 65%). In the DSC scan of poly(N-o-tolyl nadimide), two exotherms were observed at 240 and 270°C while in other samples only one exothermic transition was observed above 240°C. These exotherms disappeared in the second heating cycle. The T_g of the polymers, as determined in the second heating cycle, was highest in poly(N-o-tolyl nadimide) and lowest in poly(N-m-tolyl nadimide). The polymers were stable up to 443 ± 3°C and decomposed above this temperature in a single step. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2917–2924, 1997     

Nanoparticle‐Supported and Magnetically Recoverable Ruthenium Hydroxide Catalyst: Efficient Hydration of Nitriles to Amides in Aqueous Medium

Magnetic attraction not filtration : A magnetic nanoparticle‐supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

     

Synthesis, characterization and radiolytic properties of bis(oxalato)borate containing ionic liquids

Previously unreported bis(oxalato)borate (BOB) ionic liquids (ILs) containing imidazolium, pyridinium, and pyrrolidinium cations were prepared from the corresponding halide salts by reaction with sodium bis(oxalato)borate (NaBOB), and their properties are reported. Pulse radiolysis experiments revealed that the BOB anion scavenges solvated electrons with rate constants of 3×10⁸ M⁻¹ s⁻¹ in the ionic liquid C₄mpyrr NTf₂ and 2.8×10⁷ M⁻¹ s⁻¹ in water. This reactivity indicates that BOB ILs may be too sensitive to be used as neat solvents for nuclear separations processes in high radiation fields but may still be useful for preventing criticality while processing relatively “cold” fissile actinides.     

Nanocrystalline NaNbO3 and NaTaO3: Rietveld studies,Raman spectroscopy and dielectric properties

Nanocrystalline NaNbO₃ and NaTaO₃ have been synthesized by the reverse micellar technique for the first time. The particle size of NaNbO₃ was found to be 18 nm while that of NaTaO₃ was found to be 40 nm (much smaller size than most of the earlier reports on NaTaO₃). Rietveld refinement of X-ray diffraction data and Raman spectroscopy confirm that the nanoparticles of NaNbO₃ and NaTaO₃ have orthorhombically distorted structures with Pmc2₁ and Pbnm space groups, respectively. The dielectric constant at 25 °C of NaNbO₃ and NaTaO₃ was found to be 209 and 147 at 1 kHz, respectively. The antiferroelectric transition in NaNbO₃ shifts to lower temperature (325 °C) in the nanocrystalline solid.     

Aqueous N-heterocyclization of primary amines and hydrazines with dihalides: microwave-assisted syntheses of N-azacycloalkanes, isoindole, pyrazole, pyrazolidine, and phthalazine derivatives

[reactions: see text] The synthesis of nitrogen-containing heterocycles from alkyl dihalides (ditosylates) and primary amines and hydrazines via a simple and efficient cyclocondensation in an alkaline aqueous medium that occurs under microwave irradiation is described. This improved greener synthetic methodology provides a simple and straightforward one-pot approach to the synthesis of a variety of heterocycles, such as substituted azetidines, pyrrolidines, piperidines, azepanes, N-substituted 2,3-dihydro-1H-isoindoles, 4,5-dihydropyrazoles, pyrazolidines, and 1,2-dihydrophthalazines.     

Cobalt perchlorate hexahydrate catalyzed one-pot synthesis of dihydropyrimidin-ones/-thiones through sonochemistry and its mechanistic study using density functional theory calculations

A cobalt(II) perchlorate hexahydrate coordinated synthesis of dihydropyrimidin-ones and -thiones through sonochemistry is developed. Herein, the reaction was demonstrated as a simple, efficient, and one-pot method for synthesizing a series of interesting 3,4-dihydropyrimidin-2(1H)-ones. Further, the reaction mechanism was investigated using mass spectrometry and density functional theory calculations suggesting that a Lewis acid character of cobalt(II) perchlorate hexahydrate plays a crucial role in coordinating carbonyl functionalities and stabilizing the polar intermediates like imine–enamine which further led to cyclized dihydropyrimidin-ones and -thiones. This methodology was further explored to synthesize a gram-scale synthesis of monastrol drug, a kinase inhibitor.     

Gold Nanocages as Effective Photothermal Transducers in Killing Highly Tumorigenic Cancer Cells

Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL^?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL^?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells.     

Synthesis and properties of amphiphilic photoresponsive gelators for aromatic solvents

A sugar-based photoresponsive supergelator, N-glycosylazobenzene that shows selective gelation of aromatic solvents is described. The partial trans-cis isomerization of the azobenzene moiety allows photoinduced chopping of the entangled gel fibers to short fibers, resulting in controlled fiber length and gel-sol transition. The gelator is useful for the selective removal of toxic aromatic solvents from water.     

Facile, Selective, and Regiocontrolled Synthesis of Oxazolines and Oxazoles Mediated by ZnI(2) and FeCl(3)

An expedient method for a direct approach to the selective and regiocontrolled synthesis of 2-oxazolines and 2-oxazoles mediated by ZnI(2) and FeCl(3) is described. A Lewis acid promoted cyclization of acetylenic amide with various functionalities was well tolerated to give 2-oxazolines and 2-oxazoles in good to excellent yields under mild reaction conditions.