Using grazing incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) it has been recently demonstrated that linear fluorocarbon-hydrocarbon diblocks (FnHm) self-assemble in water/air interfaces forming elongated and circular hemimicelles. Those structures have been observed for diblocks with at least eight fluorinated carbons. Based on the lack of a collapse pressure for F6H16, and due to the fact that no stable surface pressure values are reached under compression, it has been concluded that these molecules do not form stable monolayers. It has been also suggested that F6H16 and shorter diblocks desorb from the water surface under compression. It is not easy to accept that a significant concentration of so hydrophobic molecules can be stable in aqueous solution even when the employed experimental techniques were not able to clearly detect a well defined structure on the interface. In the present work the adsorption and arrangement of F6H16 and F6H10 at the water surface are studied by molecular dynamics (MD) simulations as a function of the available area per molecule. Starting from a random mixture, the spontaneous formation of elongated hemimicelles is observed for both systems when the area per molecule is higher than approximately 50 A(2). For intermediate areas two pseudo-phases, one rich in hydrocarbons and the other with higher fluorocarbon concentration, are formed. For the systems with less than approximately 30 A(2) available per molecule the formation of multilayers is observed. This is the first time that the dynamics and structure of perfluoroalkane (PFA) films, and in particular of hemimicelles on a liquid surface, are observed and characterized at atomic level. 相似文献
A sensitive and rapid liquid chromatographic method was successfully developed and validated for the determination of sibutramine hydrochloride in bulk and capsules. Sibutramine in the presence of its degradation products was analyzed using UV detection at 225 nm. Chromatography was performed on a reversed-phase C8 (150 × 4.0 mm I.D., 5 μm) analytical column under isocratic conditions. The mobile phase was composed of acetonitrile:water (aqueous phase containing 0.3% triethylamine and pH adjusted to 7.0) (75:25, v/v) at a flow-rate of 1.1 mL min−1. No chromatographic interference was found during the analysis. Light was the stress condition which most contributed to sibutramine degradation. The method showed a linear response (r > 0.999) from 30 to 90 μg mL−1. The mean recovery for capsules was 101.2%. Inter-day assays showed relative standard deviations of 0.42 and 1.62% for bulk and capsules, respectively. The developed method is able to separate sibutramine from its major degradation products and it may be used in the quality control of this active pharmaceutical ingredient in both bulk and capsules.
The reduction of the carbon-nitrogen double bond is an important transformation. Here we report our studies on a family of chiral organic catalysts able to promote the stereoselective reduction of ketimines with trichlorosilane. The very cheap, metal-free catalysts were easily prepared in one step from commercially available products, namely a chiral aminoalcohol and picolinic acid derivatives. The catalyst structure was extensively modified in a study that allowed to identify an extremely active species, able to promote the reduction on a large variety of substrates with high efficiency (up to 95% ee). A three component methodology has been also developed, where the enantiomerically enriched amine was isolated after performing the reaction by mixing a ketone and an amine in the presence of trichlorosilane and the catalyst. Its synthetic potentiality was demonstrated by employing the present metal-free catalytic procedure in the preparation of (S)-metolachlor, a potent and widely used herbicide. 相似文献
Summary: Emulsion polymerization reactions were performed under microwave irradiation and conventional heating using anionic or cationic initiators and surfactants. Microwave irradiation promoted higher reaction rates for both initiators and surfactants, in comparison with the conventional heating. The effect of high power microwave irradiation was studied using a method of cycles of heating and cooling, where rapid polymerization reactions were obtained. In the reactions with anionic initiator and surfactant, a decrease in the particle diameters was observed with microwave heating, and even smaller particles were obtained using high power microwave irradiation. Moreover, the decrease in the particle size was acompanied by an increase in the polymer molecular weight. On the other hand, these effects were not observed for reactions with cationic initiator and surfactant. 相似文献
We describe the improvement of a novel approach to investigating hydrogen/deuterium (H/D) exchange kinetics in biomolecules
using transmission infrared spectroscopy. The method makes use of a Fourier transform infrared spectrometer coupled with a
microdialysis flow cell to determine exchange rates of labile hydrogens. With this cell system, the monitoring of exchange
reactions has been studied here as a function of some cell characteristics such as: (a) dialysis membrane surface contacting
both the H2O and D2O compartments; (b) molecular cutoff of dialysis membrane; and (c) distance between the cell-filling holes. The best improvement
has been obtained by increasing the dialysis membrane surface followed by increase of molecular cutoff. However, not significant
differences were found using various distances between filling holes. The fastest exchange rate which can be measured with
the cell system used here is found to be k = 0.41 ± 0.02 min−1, that is, about threefold greater than the one got in a previous work. This microdialysis flow cell has been used here for
the study of H/D exchange in nucleic acids with subsequent structural analysis by 2D correlation spectroscopy. 相似文献
Summary: The search of new inorganic materials with better catalytic properties is an important field of research. Reusability, efficiency and atom economy correspond to the main parameters to characterize a catalyst. In this work, we inform the effectiveness of [Cu(H2btec)(bipy)]∞ (H4btec = 1,2,4,5-benzenetetracarboxylic acid) as an heterogeneous coordination polymer catalyst for the oxidation of olefins. The catalyst exhibits good atom economy, high turnover numbers and good selectivity for a ratio of 4000/1 substrate/catalyst for cyclohexene and styrene oxidation. Furthermore, the catalyst was recycled and reused for seven consecutive cycles, retaining the structural integrity and effectiveness as catalyst in all the performed experiments. 相似文献
Summary: Binary metallocene-MAO and ternary diphenylzinc-metallocene-MAO initiator systems have been tested as initiators in the homopolymerization of styrene and also in its copolymerization with several diverse comonomers including substituted styrenes, styrene derivatives, α-olefins and dienes. Various titanocenes and zirconocenes and some exploratory experiment with hafnocene were carried out. The results indicate that titanocenes were more effective than zirconocenes in the homopolymerization of styrene while zirconocenes did better in α-olefin polymerization. It was found that titanocenes generated mainly syndiotactic polystyrene, s-PS, while zirconocenes yielded atactic polystyrene or, depending on the zirconocene, a low percentage of s-PS. For these types of initiators the polymerization process depends largely on the inductive effect of the substituents linked to the benzene ring of styrene and on its position (ortho, meta or para). Substituent multiplicity reduced markedly the effectiveness of these initiator systems. Styrene/isoprene polymerization was also studied using binary zirconocene-MAO initiator systems that yielded low conversions and also low molecular weight polymers. 相似文献
This paper tries to contribute to the well-known and lengthy discussion on whether we should allow decision makers to be inconsistent, or, to put it in another way, if intransitive decisions better represent their preferences. We will focus specifically on the multiple-criteria decision making problem, since it is one of the most usual stances where this intransitivity appears. Results from an experiment carried out with graduate students shows that, when intransitivities are removed, the preferences of decision makers are not better represented, and therefore that the effort to do so may not be justified. 相似文献