RESUMO
Deoxydehydration (DODH) reaction of glycerol (GL) and 1,2-propanediol (1,2-PD), in ionic liquids (ILs), catalyzed by methyltrioxorhenium (MTO) and Re2O7, was studied in detail. To better understand the ability of ILs to improve the catalytic performance of the rhenium catalyst, several experiments, employing eight different cations and two different anions, were carried out. Among the anions, bis(trifluoromethylsulfonyl)imide (TFSI) appears to be more appropriate than PF6 -, for its relatively lower volatility of the resulting IL. Regarding the choice of the most appropriate cation, the presence of a single aromatic ring seems to be a necessary requirement for a satisfying and convenient reactivity. With the aim to extend the recyclability of the catalyst, experiments involving the readdition of polyol to the terminal reaction mixture were carried out. Worthy of interest is the fact that the presence of the IL prevents the inertization process of the catalyst, allowing us to obtain the alkene also after a readdition of fresh polyol.
RESUMO
An amphiphilic calix[6]arene, alone or complexed with an axle to form a pseudo-rotaxane, has been embedded into liposomes prepared from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and the permeability of the membrane-doped liposomes towards Cl- ions has been evaluated by using lucigenin as the fluorescent probe. The pseudo-rotaxane promotes transmembrane transport of Cl- ions more than calix[6]arene does. Surprisingly, the quenching of lucigenin was very fast for liposomes doped with the positively charged axle alone. Molecular dynamics (MD) simulations and quantum-chemical calculations were also carried out for providing a semi-quantitative support to the experimental results.
Assuntos
Calixarenos/metabolismo , Cloretos/metabolismo , Ionóforos/metabolismo , Bicamadas Lipídicas , Lipossomos , Biologia Computacional/métodos , Simulação de Dinâmica Molecular , Relação Estrutura-AtividadeRESUMO
Biologically active prenyoxyphenylpropanoids are well known to be biosynthesized by Citrus species, for which they have been found most abundantly in fruit peels. Although several extraction methodologies have been described, the development of novel and alternative extraction processes is a field of research of current interest. In this preliminary communication, we studied the performance of the subcritical butane promoted extraction of selected oxyprenylated phenylpropanoids from grapefruit peels under a counter-current mode using a handmade extraction apparatus coupled to UHPLC analysis. The application of such a method yielded 7-isopentenyloxycoumarin, auraptene, and boropinic acid in quantities higher than those recorded for other extraction methodologies like the ultrasound- and microwave-assisted macerations (0.234, 1.035, and 0.211â¯mg/g of dry extract respectively). The use of subcritical butane as the extraction solvent for oxyprenylated phenylpropanoids is reported herein for the first time and can be easily adopted for several other food matrices.
Assuntos
Butanos/química , Cromatografia Líquida de Alta Pressão/métodos , Citrus paradisi/química , Extratos Vegetais/química , Cumarínicos/química , Frutas/químicaRESUMO
This paper contains data of water capacity (in terms of w 0 = molwater/molsurfactant) in reverse micelles formed by several commercial and non-commercial cationic surfactants in cyclopentane, petroleum ether, and iso-octane. Also reported are hydrodynamic diameters of the respective reverse micelles formed. Tested surfactants were (i) single-chained cationics: cetyl benzyl diethanolammonium bromide (CBDB), cetyl benzyl dimethylammonium bromide (CBMB), cetyl dibutyl ethanolammonium bromide (CDBEB), cetyl cyclohexyl dimethylammonium bromide (CCDB); and (ii) twin-chained cationics: didodecyl dimethylammonium chloride (DDMC), didodecyl diethylammonium bromide (DDEB), didodecyl dipropylammonium bromide (DDPB), didodecyl diethylammonium chloride (DDEC), dodecyl benzyl dimethylammonium bromide (DBDMB). Also reported are sizes of reverse micelles as determined by dynamic light scattering.
RESUMO
HYPOTHESIS: Clathrate hydrates of hydrogen form at relatively low pressures (e.g., ca. 10â¯MPa) when a co-former compound is added. In that case, however, the gravimetric amount of stored hydrogen drops to less than 1â¯wt% from ca. 5.6â¯wt% without a co-former. Another factor hindering the entrapment of hydrogen into a clathrate matrix appears to be of a kinetic origin, in that the mass transfer of hydrogen into clathrates is limited by the macroscopic scale of the gas-water interfaces involved in their formation. Thus, the enhanced formation of binary (hydrogenâ¯+â¯co-former) hydrates would represent a major achievement in the attempt to exploit those materials as a convenient means for storing hydrogen. EXPERIMENTS: Here, we present a simple process for the enhanced formation of binary hydrates of hydrogen and several co-formers, which is based on the use of reverse micelles for reducing the size of hydrate-forming gas-water interfaces down to tens of nanometers. This reduction of particle size allowed us to reduce the kinetic hindrance to hydrate formation. FINDINGS: The present process was able to (i) enhance the kinetics of the formation process; and (ii) assist clathrate formation when using water-insoluble coformers (e.g., cyclopentane, tetrahydrothiophene).
RESUMO
The rhenium dioxide anion [ReO2](-) reacts with carbon dioxide in a linear ion trap mass spectrometer to produce [ReO3](-) corresponding to activation and cleavage of a C-O bond. Isotope labeling experiments using [Re(18)O2](-) reveal that (18)O/(16)O scrambling does not occur prior to cleavage of the C-O bond. Density functional theory calculations were performed to examine the mechanism for this oxygen atom abstraction reaction. Because the spins of the ground states are different for the reactant and product ions ((3)[ReO2](-) versus (1)[ReO3](-)), both reaction surfaces were examined in detail and multiple [O2Re-CO2](-) intermediates and transition structures were located and minimum energy crossing points were calculated. The computational results show that the intermediate [O2Re(η(2)-C,O-CO2)](-) species most likely initiates C-O bond activation and cleavage. The stronger binding affinity of CO2 within this species and the greater instabilities of other [O2Re-CO2)](-) intermediates are significant enough that oxygen atom exchange is avoided.
RESUMO
The ion-molecule reactions of the rhenium oxide anions, [ReOx](-) (x = 2 - 4) with the organic substrates methane, ethene, methanol and acetic acid have been examined in a linear ion trap mass spectrometer. The only reactivity observed was between [ReO(2)](-) and acetic acid. Isotope labelled experiments and high-resolution mass spectrometry measurements were used to assign the formulas of the ionic products. Collision-induced dissociation and ion-molecule reactions with acetic acid were used to probe the structures of the mass-selected primary product ions. Density functional theory calculations [PBE0/LanL2DZ6-311+G(d)] were used to suggest possible structures. The three primary product channels observed are likely to arise from the formation of: the metallalactone [ReO(2)(CH(2)CO(2))](-) (m/z 277) and H(2); [CH(3)ReO(2)(OH)](-) (m/z 251) and CO; and [ReO(3)](-) (m/z 235), H(2) and CH(2)CO.