Cu-nanoparticles: a chemoselective catalyst for the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile

A novel method for effecting the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile using Cu-nanoparticles is described. The method features the use of 10 mol % Cu (14-17 nm) nanoparticles under mild reaction conditions to afford the addition products in good to excellent yields. The Cu-nanoparticles selectively catalysed the aza-Michael reaction of N-alkyl- and N-arylpiperazines in the presence of aromatic amino or aliphatic hydroxy groups.     

A rapid and simple route for the synthesis of lead and palladium nanoparticles in tetrazolium based ionic liquid

In the present work, we report a novel method for the synthesis of palladium and lead nanoparticles by the reduction method in tetrazolium ring based ionic liquid. Palladium and lead nanoparticles so-prepared were well characterized by powder X-ray diffraction measurements (pXRD), transmission electron microscopy (TEM) and quasi elastic light scattering (QELS) techniques. Powder X-ray diffraction (pXRD) analysis revealed all relevant Bragg's reflection for crystal structure of palladium and lead. Powder X-ray diffraction plots also revealed no oxidized material of palladium and lead nanoparticles. TEM showed nearly uniform distribution of the particles in methanol and confirmed by QELS. Typical applications of palladium nanoparticles include in vitro use and sensor design applications. Palladium nanoparticles is also ideal for spin coating, self-assembly and monolayer formation. Palladium nanoparticles can also be considered as potential new catalysts.     

Enantiospecific formal total syntheses of (-)-salicylihalamides A and B from D-glucose and L-rhamnose

[reaction: see text] Two formal chiral pool syntheses of the (-)-salicylihalamides A and B were achieved from commercially available 1,2,5,6-diacetone-d-glucose and l-rhamnose.     

Cross-linked polyvinylpyrrolidone nanoparticles: a potential carrier for hydrophilic drugs

Injectable hydrogel polymeric nanoparticles of polyvinylpyrrolidone cross-linked with N,N'-methylene bis-acrylamide and encapsulating water-soluble macromolecules such as FITC-dextran (FITC-Dx) have been prepared in the aqueous cores of reverse micellar droplets. These particles are 100 nm and below in diameter with a narrow size distribution. When dispersed in aqueous buffer these particles appear to be transparent and give an optically clear solution. Lyophilized powder of these nanoparticles is redispersable in aqueous buffer without any change in the size and morphology of the particles. The efficiency of FITC-Dx entrapment by these nanoparticles is high (>70%) and depends on the amount of cross-linking agent present in the polymeric material. The release of the entrapped molecules from these nanoparticles depends on the degree of cross-linking of the polymer, particle size, pH of the medium, and extent of loading, as well as temperature.     

Activity and Conformation of Yeast Alcohol Dehydrogenase (YADH) Entrapped in Reverse Micelles

Yeast alcohol dehydrogenase (YADH) solubilized in reverse micelles of aerosol OT (i.e., AOT or sodium bis (2-ethyl hexyl) sulfosuccinate) in isooctane has been shown to be catalytically more active than that in aqueous buffer under optimum conditions of pH, temperature, and water content in reverse micelles. Studies of the secondary structure conformational changes of the enzyme in reverse micelles have been made from circular dichroism spectroscopy. It has been seen that the conformation of YADH in reverse micelles is extremely sensitive to pH, temperature, and water content. A comparison has been made between the catalytic activity of the enzyme and the α-helix content in the conformation and it has been observed that the enzyme is most active at the maximum α-helix content. While the β-sheet content in the conformation of the entrapped enzyme was found to be dependent on the enzyme–micelle interface interaction, the α-helix and random coil conformations are governed by the degree of entrapment and the extent of rigidity provided by the micelle core to the enzyme structure.     

Formal total syntheses of the (-)-salicylihalamides A and B from D-glucose and L-rhamnose

[reaction: see text] Two formal total syntheses of the (-)-salicylihalamides, based on chiral pool approaches, are reported. D-glucose and L-rhamnose were used to prepare advanced intermediates 23 and 54, which can be converted in three or four steps, respectively, to the target compounds. The synthesis of 23 from a known D-glucose-derivative was accomplished in 12 steps and 17% overall yield, and the synthesis of 54 from a known L-rhamnose-derivative was done in nine steps and 6% overall yield. A key step in the synthesis was a ring-closing metathesis reaction to prepare the macrocyclic ring system. It was demonstrated that the phenolic protecting group was critical for inducing the preferential formation of the desired E isomer. It was further shown that the protecting group at the C13 hydroxyl group had no significant influence on the E:Z ratio during the ring-closing metathesis reaction.     

Influence of CuO catalyst in the nanoscale range on SnO2 surface for H2S gas sensing applications

The dispersal of CuO catalyst on the surface of the semiconducting SnO₂ film is found to be of vital importance for improving the sensitivity and the response speed of a SnO₂ gas sensor for H₂S gas detection. Ultra-thin CuO islands (8 nm thin and 0.6 mm diameter) prepared by evaporating Cu through a mesh and subsequent oxidation yield a fast response speed and recovery. Ultimately nanoparticles of Cu (average size = 15 nm) prepared by a chemical technique using a reverse micelle method involving the reduction of Cu(NO₃)₂ by NaBH₄ exhibited significant improvement in the gas sensing characteristics of SnO₂ films. A fast response speed of ∼14 s and a recovery time of ∼60 s for trace level ∼20 ppm H₂S gas detection have been recorded. The sensor operating temperature (130° C) is low and the sensitivity (S = 2.06 × 10³) is high. It is found that the spreading over of CuO catalyst in the nanoscale range on the surface of SnO₂ allows effective removal of excess adsorbed oxygen from the uncovered SnO₂ surface due to spill over of hydrogen dissociated from the H₂S-CuO interaction.     

Divergent asymmetric synthesis of hexahydrobenzophenanthridine dopamine D1 agonists,A-86929, and dihydrexidine

A divergent and scalable asymmetric synthesis of the dopamine D1 agonists, A-86929, and dihydrexidine with high diastereo- and enantioselectivity was accomplished from Weinreb amide 8 derived from inexpensive and easily available l-serine. The synthesis of A-86929 involves only one chromatographic purification.     

Recyclable nanoparticulate copper mediated synthesis of naphthoxazinones in PEG-400: a green approach

An efficient methodology employing copper nanoparticles for the preparation of 2-naphthol condensed 1,3-oxazinone derivatives employing one-pot condensation reaction in the presence of K₂CO₃ and copper nanoparticles in PEG-400 is described which offers several advantages, viz. high yields, clean reaction, short reaction times, recyclability of the catalyst and simple workup procedure. PEG-400 was found to be the best solvent out of a range of solvents examined for this scheme. Moreover, PEG could stabilize the nanoparticles from oxidation and thus could increase the catalyst efficiency by escalating the TON (Turn over Number) and TOF (Turn over Frequency) of the catalyst, making the protocol greener, eco-friendly and environmentally benign.     

Molecular iodine in [bmim][BF4]: a highly efficient green catalytic system for one-pot synthesis of 1,3-oxathiolan-5-one

Aldehydes and mercaptoacetic acid are coupled in the presence of a catalytic amount of economical and non-toxic molecular iodine in [bmim][BF₄] ionic liquid under mild conditions to afford the corresponding 1,3-oxathiolan-5-one in excellent yields. Molecular iodine acts faster in ionic liquids when compared to conventional solvents such as DMSO, DMF, ethyl acetate, and acetonitrile. The recovered ionic liquids can be recycled in subsequent reactions with consistent activity.