Adsorption of polar and nonpolar compounds onto complex nanooxides with silica, alumina, and titania.

Adsorption of low-molecular adsorbates (nonpolar hexane, nitrogen, weakly polar acetonitrile, and polar diethylamine, triethylamine, and water) onto individual (silica, alumina, titania), binary (silica/alumina (SA), silica/titania (ST)), and ternary (alumina/silica/titania, AST) fumed oxides was studied to analyse the effects of morphology and surface composition of the materials. Certain aspects of the interfacial phenomena dependent on the structural characteristics of oxides were analysed using calorimetry, (1)H NMR, and Raman spectroscopies, XRD, and ab initio quantum-chemical calculations. The specific surface area S(BET,X)-to-S(BET,N(2)) ratio (X is an organic adsorbate) changes from 0.68 for hexane adsorbed onto amorphous SA8 (degassed at 200 degrees C) to 1.85 for acetonitrile adsorbed onto crystalline alumina (degassed at 900 degrees C). These changes are relatively large because of variations in orientation, lateral interactions, and adsorption compressing of molecules adsorbed onto oxide surfaces. Larger S(BET,X)/S(BET,N(2)) values are observed for mixed oxides with higher crystallinity of titania or/and alumina phases in larger primary nanoparticles with greater surface roughness and hydrophilicity. Polar adsorbates can change the structure of aggregates of oxide nanoparticles that can, in turn, affect the results of adsorption measurements.

Synthesis of diethylamine-functionalized soybean oil.

Specialty chemicals based on renewable resources are desirable commodities due to their eco-friendly nature and "green" product characteristics. These chemicals can demonstrate physical and chemical properties comparable to those of conventional petroleum-based products. Suitably functionalized amines in the triacylglycerol structure can function as an antioxidant, as well as an antiwear/antifriction agent. In addition, the amphiphilic nature of seed oils makes them an excellent candidate as base fluid. The reaction of amine and epoxidized seed oils in the presence of a catalyst almost always leads to different intra/intermolecular cross-linked products. In most cases, the triacylglycerol structure is lost due to disruption of the ester linkage. Currently, there is no reported literature describing the aminolysis of vegetable oil without cross-linking. Here the epoxy group of the epoxidized soybean oil has been selectively reacted with amines to give amine-functionalized soybean oil. The optimization procedure involved various amines and catalysts for maximum aminolysis, without cross-linking and disruption of the ester linkage. Diethylamine and ZnCl2 were found to be the best. NMR, IR, and nitrogen analysis were used to characterize the products.

Analysis of ephedra-alkaloids using sweeping and cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography methods.

Two stacking methods of capillary electrophoresis (CE) were developed for the separation of very dilute solutions of ephedra-alkaloids, namely ephedrine, pseudoephedrine, methylephedrine, methylpseudoephedrine, norephedrine, and norpseudoephedrine. A sweeping method which uses a carrier comprised of phosphoric acid, sodium dodecyl sulfate (SDS), diethylamine and acetonitrile permits the detection of the alkaloids down to the 10(-1) microg/mL level, and the cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography (CSEI-Sweep-MEKC) method using phosphoric acid, SDS, and acetronitrile as electrolytes can detect down to the 10(-3) microg/mL level. The former requires the conductance of the sample solution to be adjusted beforehand, and only five peaks were observed, two of which were overlapped. The latter is capable of separating the six alkaloids but has a somewhat poorer reproducibility. Using an optimized injection time, it was found that the more diluted a solution is, the greater the sweeping effect will be. The CSEI-Sweep-MEKC method with a 600 s injection time and a 10(-1) microg/mL solution concentration provides an amplification effect of approximately 10(4). The method is suitable for analyses of dilute herb drug extracts and mouse sera. The effect of buffers on the separation and validation of the methods in this study are also discussed.

Molecular complexes of iron violurate with donor amines.

The acceptor character of iron violurate complex was studied by examining the electronic, vibrational and 1H-nmr spectra of the charge transfer molecular complexes formed between the iron violurate as pi-acceptor and some amines as n-donors. Elemental analysis and spectral results establishes 1:2 stoichiometry of the adducts. The study has been conducted at different temperatures. Values of delta G degree, delta H degree and delta S degree have been calculated from the self-consistent values of the formation constants (KCT). Ionization potentials of the donors have been calculated and the solvent effect on the KCT values is discussed. The antibacterial and antifungal effects of the molecular complexes were studied.