Gas-liquid selective oxidations with oxygen under explosive conditions in a micro-structured reactor

The gas-liquid oxidation of cyclohexane is performed at high temperature (>200 degrees C) and pressure (up to 25 bar) using pure oxygen in a Pyrex capped silicon etched microreactor which allows convenient screen reaction conditions well above the flammability limit.     

Light scattering studies of amphiphilic drugs promethazine hydrochloride and imipramine hydrochloride in aqueous electrolyte solutions

Two amphiphilic drugs, promethazine hydrochloride (PMT) and imipramine hydrochloride (IMP), have been studied using both static and dynamic light scattering techniques. Due to having rigid tricyclic hydrophobic moieties in their molecules, these drugs show interesting association behavior. The static light scattering (SLS) measurements show that the self-association commenced above a well-defined critical micellar concentration ( cmc), which decreases with increasing NaBr concentration. The Gibbs energy of micellization, DeltaG(0)M, in all cases, is negative. The colloidal stability of the system in terms of the interparticle interaction at different NaBr concentrations was studied using the dynamic light scattering (DLS) technique. The experimentally evaluated interparticle interaction parameter ( k D ) was compared with the Derjaguin-Landau-Verwey-Overbeek (DLVO) model. Interestingly, these two drugs with similar molecular structure show difference in their interparticle interactions, e.g., PMT showed complete agreement with the DLVO model whereas IMP showed clear deviation from this model at lower concentrations and agreement at higher concentrations of NaBr.     

Phosphite mediated asymmetric N to C migration for the synthesis of chiral heterocycles from primary amines

A phosphite mediated stereoretentive C–H alkylation of N-alkylpyridinium salts derived from chiral primary amines was achieved. The reaction proceeds through the activation of the N-alkylpyridinium salt substrate with a nucleophilic phosphite catalyst, followed by a base mediated [1,2] aza-Wittig rearrangement and subsequent catalyst dissociation for an overall N to C-2 alkyl migration. The scope and degree of stereoretention were studied, and both experimental and theoretical investigations were performed to support an unprecedented aza-Wittig rearrangement–rearomatization sequence. A catalytic enantioselective version starting with racemic starting material and chiral phosphite catalyst was also established following our understanding of the stereoretentive process. This method provides efficient access to tertiary and quaternary stereogenic centers in pyridine systems, which are prevalent in drugs, bioactive natural products, chiral ligands, and catalysts.

N-Alkylpyridinium salt of chiral amines undergoes phosphite mediated stereoretentive migrations to generate chiral alkylpyridines. The role of phosphite on reactivity and stereoselectivity were examined to achieve a catalytic asymmetric version.     

Discotic ionic liquid crystals of triphenylene as dispersants for orienting single-walled carbon nanotubes

Orient and conduct: Triphenylene-based discotic ionic liquid crystals (ILCs) with six imidazolium ion pendants can disperse pristine single-walled carbon nanotubes (SWNTs). When the ILC is columnarly assembled, doping with SWNTs results in macroscopic homeotropic columnar orientation. Combination of shear and annealing treatments gives rise to three different orientation states, which determine the anisotropy of electrical conduction.     

Reusable amine-based structural motifs for green house gas (CO2) fixation

A series of compounds with an amine based structural motif (ASM) have been synthesized for efficient atmospheric CO(2) fixation. The H-bonded ASM-bicarbonate complexes were formed with an in situ generated HCO(3)(-) ion. The complexes have been characterized by IR, (13)C NMR, and X-ray single-crystal structural analysis. ASM-bicarbonate salts have been converted to pure ASMs in quantitative yield under mild conditions for recycling processes.     

Self‐Assembly of a Mononuclear [FeIII(L)(EtOH)2] Complex Bearing an n‐Dodecyl Chain on Solid Highly Oriented Pyrolytic Graphite Surfaces

The synthesis and structures of the N‐[(2‐hydroxy‐3‐methyl‐5‐dodecylphenyl)methyl]‐N‐(carboxymethyl)glycine disodium salt (H L ) ligand and its neutral mononuclear complex [Fe^III( L )(EtOH)₂] ( 1 ) are reported. Structural and electronic properties of 1 were investigated by using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy (CITS) techniques. These studies reveal that molecules of 1 form well‐ordered self‐assemblies when deposited on a highly oriented pyrolytic graphite (HOPG) surface. At low concentrations, single or double chains (i.e., nanowires) of the complex were observed, whereas at high concentration the complex forms crystals and densely packed one‐dimensional structures. In STM topographies, the dimensions of assemblies of 1 found on the surface are consistent with dimensions obtained from X‐ray crystallography, which indicates the strong similarities between the crystal form and surface assembled states. Double chains are attributed to hydrogen‐bonding interactions and the molecules align preferentially along graphite defects. In the CITS image of complex 1 a strong tunneling current contrast at the positions of the metal ions was observed. These data were interpreted and reveal that the bonds coordinating the metal ions are weaker than those of the surrounding ligands; therefore the energy levels next to the Fermi energy of the molecule should be dominated by metal‐ion orbitals.     

Nanosized nickel oxide particles and modification with poly(methyl methacrylate)

In recent years, there is an increasing interest in the fabrication of inorganic–organic materials considering the remarkable change and improvement in properties. In this investigation, nanosized nickel oxide (NiO) particles were first prepared by calcination of nickel hydroxide precursor obtained by a simple liquid‐phase process. Mixed phases of NiO and nickel hydroxide were present as the calcination temperature was lower than 250°C. Non‐stoichiometric NiO was formed between 250°C and 350°C, and a pure NiO was obtained as the temperature reached 500°C. The surface characteristics of NiO particles were evaluated by measuring the adsorption behavior of anionic and cationic surfactants and some biomolecules. NiO/poly(methyl methacrylate) composite particles were then prepared using variable NiO/methyl methacrylate (MMA) ratio by seeded emulsion polymerization. The efficiency of NiO incorporation in the composite increased as the MMA content was increased in the recipe. The composite particles were colloidally stable, and the obtained particles were characterized by Fourier transform infrared, scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectra. Copyright © 2011 John Wiley & Sons, Ltd.     

Enzymeless determination of total sugar by luminol–tetrachloroaurate chemiluminescence on chip to analyze food samples

Chemiluminescence (CL) emission from luminol–tetrachloroaurate ([AuCl₄]^?) system studied in presence of monosaccharide sugars such as glucose and fructose was investigated on a microfluidic chip fabricated by the soft lithography technique. CL emission from the luminol–[AuCl₄]^? system at 430?nm was intensified remarkably by the catalytic activity of glucose and fructose at room temperature. Under optimized conditions, the CL emission intensity of the system was found to be linearly related to the concentration of the sugars. Based on this observation, nonenzymatic determination of total sugar (glucose, fructose, or hydrolyzable sucrose) was performed in a rapid and sensitive analytical method. The results revealed that the linearity ranged from 9 to 1,750?μM for glucose and 80 to 1,750?μM for fructose, with a limit of detection of 0.65 and 0.69?μM, respectively. The relative standard deviations determined at 250?μM based on six repetitive injections were 1.13 and 1.15?% for glucose and fructose, respectively. The developed method was successfully applied for determination of the total sugar concentration in food and beverages.

(1)H-(13)C INEPT MAS NMR correlation experiments with (1)H-(1)H mediated magnetization exchange to probe organization in lipid biomembranes

Two-dimensional (1)H-(13)C INEPT MAS NMR experiments utilizing a (1)H-(1)H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via (1)H-(1)H dipolar couplings but with (13)C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close (1)H-(1)H dipolar contacts versus longer-range inter-molecular (1)H-(1)H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures.