A new multicomponent reaction catalyzed by a [Lewis Acid](+)[Co(CO)(4)](-) catalyst: stereospecific synthesis of 1,3-oxazinane-2,4-diones from epoxides, isocyanates, and CO

The use of mechanistic information to develop a new, catalytic multicomponent reaction is described. The complex [(salph)Al(THF)2]+[Co(CO)4]- (1, salph = N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneimine), THF = tetrahydrofuran), which is known to carbonylate epoxides, aziridines, and beta-lactones, was used to catalyze the synthesis of 1,3-oxazinane-2,4-diones from epoxides, isocyanates, and CO. Under optimized conditions, the reaction was both selective and high-yielding. 1,3-Oxazinane-2,4-diones were synthesized from a variety of epoxides and isocyanates, including some epoxides that do not undergo simple ring-expansion carbonylation. The best results were obtained using highly electrophilic isocyanates. The mechanism of the multicomponent reaction was investigated using labeling and stereochemistry, and the data obtained were consistent with the 1-catalyzed formation of beta-lactone and 1,3-oxazinane-2,4-dione from a common intermediate.     

Immunoaffinity in-tube solid phase microextraction coupled with liquid chromatography-mass spectrometry for analysis of fluoxetine in serum samples

The inherent selectivity of the antibody was combined with in-tube solid-phase microextraction by immobilization of the antibody into the fused silica capillary. A sensitive, selective, and reproducible immunoaffinity in-tube solid-phase microextraction coupled with liquid chromatography-mass spectrometry (in-tube SPME/LC-MS) method was developed, and validated for fluoxetine analysis in human serum. Important factors in the optimization of in-tube SPME variables, as well as the evaluation of the immunoaffinity capillary capacity are discussed. The in-tube SPME/LC-MS method presented a limit of quantitation of 5.00 ng/mL, and precision intra-assays with RSDs lower than 5%. The response of the in-tube SPME/LC-MS method for fluoxetine was linear over a dynamic range from 5.00 to 50.00 ng/mL, with correlation coefficients better than 0.998. Based on analytical validation it was demonstrated that in-tube SPME/LC-MS method offers high sensitivity, selectivity, and enough reproducibility to permit the quantification of fluoxetine in human serum at therapeutic levels. Thus, the proposed SPME/LC method can be useful tool to determine fluoxetine serum concentrations in patients receiving therapeutic dosages.     

Magnesium borohydride complexed by tetramethylethylenediamine

A complex of magnesium borohydride, Mg(BH4)2.Me2NC2H4NMe2, has been synthesized and structurally characterized. This monomer complex has a pseudotetrahedral geometry around the Mg atom with tridentate BH4 groups and short Mg...B distances.     

Brillouin-scattering determination of the acoustic properties and their pressure dependence for three polymeric elastomers

The acoustic properties of three polymer elastomers, a cross-linked poly(dimethylsiloxane) (Sylgard 184), a cross-linked terpolymer poly(ethylene-vinyl acetate-vinyl alcohol), and a segmented thermoplastic poly(ester urethane) copolymer (Estane 5703), have been measured from ambient pressure to approximately 12 GPa by using Brillouin scattering in high-pressure diamond anvil cells. The Brillouin-scattering technique is a powerful tool for aiding in the determination of equations of state for a variety of materials, but to date has not been applied to polymers at pressures exceeding a few kilobars. For the three elastomers, both transverse and longitudinal acoustic modes were observed, though the transverse modes were observed only at elevated pressures (>0.7 GPa) in all cases. From the Brillouin frequency shifts, longitudinal and transverse sound speeds were calculated, as were the C(11) and C(12) elastic constants, bulk, shear, and Young's moduli, and Poisson's ratios, and their respective pressure dependencies. P-V isotherms were then constructed, and fit to several empirical/semiempirical equations of state to extract the isothermal bulk modulus and its pressure derivative for each material. Finally, the lack of shear waves observed for any polymer at ambient pressure, and the pressure dependency of their appearance is discussed with regard to instrumental and material considerations.     

Determination of static microstructure of dilute and concentrated suspensions of anisotropic particles by ultra-small-angle X-ray scattering

Ultra-small-angle X-ray scattering was performed on suspensions of anisotropic polystyrene particles of varying degrees of anisotropy. The wave vector dependence of particle form factors is well described by a model developed by Debye for the scattering from fused spheres. As volume fraction is raised, all suspensions undergo a disorder/order phase transition. The scattering from disordered and ordered suspensions of anisotropic particles is the same as that of spheres up to volume fractions of 0.45, suggesting that, in the dilute crystalline phase, the anisotropic particles order into a rotator or plastic crystal phase, where the particle centers of mass are ordered, but the particle directors are randomly distributed. Further increase in particle volume fraction leads to differences in scattering between homonuclear dicolloids and spheres, implying that the homonuclear dicolloids form a body-centered tetragonal phase with both positional and directional order. This conclusion is supported by real-space imaging of dried films of the particles.     

Hexosome and hexagonal phases mediated by hydration and polymeric stabilizer

In this research, we studied the factors that control formation of GMO/tricaprylin/water hexosomes and affect their inner structure. As a stabilizer of the soft particles dispersed in the aqueous phase, we used the hydrophilic nonionic triblock polymer Pluronic 127. We demonstrate how properties of the hexosomes, such as size, structure, and stability, can be tuned by their internal composition, polymer concentration, and processing conditions. The morphology and inner structure of the hexosomes were characterized by small-angle X-ray scattering, cryo-transmission electron microscope, and dynamic light scattering. The physical stability (to creaming, aggregation, and coalescence) of the hexosomes was further examined by the LUMiFuge technique. Two competing processes are presumed to take place during the formation of hexosomes: penetration of water from the continuous phase during dispersion, resulting in enhanced hydration of the head groups, and incorporation of the polymer chains into the hexosome structure while providing a stabilizing surface coating for the dispersed particles. Hydration is an essential stage in lyotropic liquid crystal (LLC) formation. The polymer, on the other hand, dehydrates the lipid heads, thereby introducing disorder into the LLC and reducing the domain size. Yet, a critical minimum polymer concentration is necessary in order to form stable nanosized hexosomes. These competing effects require the attention of those preparing hexosomes. The competition between these two processes can be controlled. At relatively high polymer concentrations (1-1.6 wt % of the total formulation of the soft particles), the hydration process seems to occur more rapidly than polymer adsorption. As a result, smaller and more stable soft particles with high symmetry were formed. On the other hand, when the polymer concentration is fixed at lower levels (<1.0 wt %), the homogenization process encourages only partial polymer adsorption during the dispersion process. This adsorption is insufficient; hence, maximum hydration of the surfactant head group is reached prior to obtaining full adsorption, resulting in the formation of less ordered hexosomes of larger size and lower stability.     

Periodic mesoporous organosilicas with multiple bridging groups and spherical morphology

Bi- and trifunctional periodic mesoporous organosilicas (PMOs) with phenylene, thiophene, and ethane bridging groups were synthesized using 1,2-bis(triethoxysilyl)ethane (BTEE), 1,4-bis(triethoxysilyl)benzene (BTEB), and 2,5-bis(triethoxysilyl)thiophene (BTET) organosilica precursors and a poly(ethylene oxide)-poly(D,L-lactic acid-co-glycolic acid)-poly(ethylene oxide) (PEO-PLGA-PEO) triblock copolymer template under low acidic conditions. The PMO samples with different concentrations of organic bridging groups were obtained in the form of spherical particles having average diameters of 2-3 mum and 2D hexagonal (p6m) mesostructure with pore diameters of 7.3-8.4 nm. The particle morphology and chemistry of pore walls were tailored using different mixtures of organosilica precursors. Adsorption and structural properties of the aforementioned PMOs have been studied by nitrogen adsorption and small-angle X-ray scattering, whereas their framework chemistry was quantitatively analyzed by solid-state 13C and 29Si MAS NMR.     

Indonesian propolis: chemical composition, biological activity and botanical origin

From a biologically active extract of Indonesian propolis from East Java, 11 compounds were isolated and identified: four alk(en)ylresorcinols (obtained as an inseparable mixture) (1-4) were isolated for the first time from propolis, along with four prenylflavanones (6-9) and three cycloartane-type triterpenes (5, 10 and 11). The structures of the components were elucidated based on their spectral properties. All prenylflavanones demonstrated significant radical scavenging activity against diphenylpicrylhydrazyl radicals, and compound 6 showed significant antibacterial activity against Staphylococcus aureus. For the first time Macaranga tanarius L. and Mangifera indica L. are shown as plant sources of Indonesian propolis.     

Stress and heat flux for arbitrary multibody potentials: a unified framework

A two-step unified framework for the evaluation of continuum field expressions from molecular simulations for arbitrary interatomic potentials is presented. First, pointwise continuum fields are obtained using a generalization of the Irving-Kirkwood procedure to arbitrary multibody potentials. Two ambiguities associated with the original Irving-Kirkwood procedure (which was limited to pair potential interactions) are addressed in its generalization. The first ambiguity is due to the nonuniqueness of the decomposition of the force on an atom as a sum of central forces, which is a result of the nonuniqueness of the potential energy representation in terms of distances between the particles. This is in turn related to the shape space of the system. The second ambiguity is due to the nonuniqueness of the energy decomposition between particles. The latter can be completely avoided through an alternate derivation for the energy balance. It is found that the expressions for the specific internal energy and the heat flux obtained through the alternate derivation are quite different from the original Irving-Kirkwood procedure and appear to be more physically reasonable. Next, in the second step of the unified framework, spatial averaging is applied to the pointwise field to obtain the corresponding macroscopic quantities. These lead to expressions suitable for computation in molecular dynamics simulations. It is shown that the important commonly-used microscopic definitions for the stress tensor and heat flux vector are recovered in this process as special cases (generalized to arbitrary multibody potentials). Several numerical experiments are conducted to compare the new expression for the specific internal energy with the original one.