Large apparent interfacial slippage at polyelectrolyte-perfluorocarbon interfaces on a quartz crystal resonator

The apparent negative areal mass densities obtained for a polyelectrolyte multilayer on a quartz crystal resonator in contact with four different perfluorocarbon liquids are explained by the interfacial slippage between the multilayer and the liquids. It is shown that the zone of interfacial slipping can be conveniently treated as a separate layer with distinct physical parameters. Three models of slippage were taken into a closer study. In the first model, the so-called de Gennes model, a very thin gas-filled cavity is formed between the moving phase and the stationary phase. The second model is based on the slipping layer consisting of water. In the third model, the so-called "true slipping" model, it is assumed that the particle velocity has a discontinuity at the interface. In each case, the slipping admittances and slippage lengths as well as the corrected areal mass densities were calculated from the experimental data. Although no unambiguous experimental evidence was found to favor strongly any of these three models, the slightly smaller variation in the slipping admittance and the areal mass density seems to give more credibility to the de Gennes model.     

Antitrypanosomal activity of Brazilian propolis from Apis mellifera

Extracts from different samples of Brazilian propolis were obtained by Soxhlet extraction or maceration at room temperature using ethanol, water, and accombination of both solvents. Analysis of their composition using HPLC revealed that no major differences were seen when a propolis sample was subject to different extraction methods. The activity of the 15 extracts was assayed against bloodstream trypomastigotes of Trypanosoma cruzi, the etiologic agent of Chagas' disease. Multivariate analysis was applied to evaluate the efficiency of the different extracts and the trypanocidal activity. The extracts could be divided into two groups. In the first, in which, extracts were obtained by reflux in Soxhlet using 100% ethanol, there was a lower content of bioactive compounds and consequently lower trypanocidal activity. Extract 136-Et100 stands out in this group, since it had the highest levels of bioactive compounds together with highest activity against the parasite when compared with all other extracts. The second group comprises extracts with intermediate levels of bioactive compounds and higher activity against T. cruzi.     

Existence and stability of new nanoreactors: highly swollen hexagonal liquid crystals

We report the preparation of direct hexagonal liquid crystals, constituted of oil-swollen cylinders arranged on a triangular lattice in water. The volume ratio of oil over water, rho can be as large as 3.8. From the lattice parameter measured by small-angle X-ray scattering, we show that all the oil is indeed incorporated into the cylinders, thus allowing the diameter of the cylinders to be controlled over one decade range, provided that the ionic strength of the aqueous medium and rho are varied concomitantly. These hexagonal swollen liquid crystals (SLCs) have been first reported with sodium dodecyl sulfate as anionic surfactant, cyclohexane as solvent, 1-pentanol as co-surfactant, and sodium chloride as salt (Ramos, L.; Fabre, P. Langmuir 1997, 13, 13). The stability of these liquid crystals is investigated when the pH of the aqueous medium or the chemical nature of the components (salt and surfactant) is changed. We demonstrate that the range of stability is quite extended, rendering swollen hexagonal phases potentially useful for the fabrication of nanomaterials. As illustrations, we finally show that gelation of inorganic particles in the continuous aqueous medium of a SLC and polymerization within the oil-swollen cylinders of a SLC can be conducted without disrupting the hexagonal order of the system.     

Dynamic ionization of water under extreme conditions

Raman spectroscopy in a laser heated diamond anvil cell and first principles molecular dynamics simulations have been used to study water in the temperature range 300 to 1500 K and at pressures to 56 GPa. We find a substantial decrease in the intensity of the O-H stretch mode in the liquid phase with pressure, and a change in slope of the melting line at 47 GPa and 1000 K. Consistent with these observations, theoretical calculations show that water beyond 50 GPa is "dynamically ionized" in that it consists of very short-lived (<10 fs) H2O, H3O+, and OH- species, and also that the mobility of the oxygen ions decreases abruptly with pressure, while hydrogen ions remain very mobile. We suggest that this regime corresponds to a superionic state.     

Polymerization of formic acid under high pressure

We report Raman, infrared, and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid (FA) under pressure up to 50 GPa. We find an infinite chain Pna2(1) structure to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intrachain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of long-range order at pressures above 40 GPa, with a large hysteresis upon decompression. We attribute this behavior to a three-dimensional polymerization of FA.     

New hybrid organic-inorganic nanocomposites based on functional [Ti16O16(OEt)24(OEMA)8] nano-fillers

New hybrid nanocomposites based on a methacrylate functionalized titanium-oxo cluster as nano-cross-linker show improved mechanical properties, optical transparency and photochromic activity.     

"Click chemistry"en route to pseudo-starch

Rapid assembly of starch fragment analogues was achieved using "click chemistry". Specifically, two hexadecasaccharide mimics containing two parallel maltoheptaosyl chains linked via [1,2,3]-triazoles to a maltose core were synthesized using Cu(i)-catalyzed [3 + 2] dipolar cycloaddition of azido saccharides and 6,6'- and 4',6'-dipropargylated p-methoxyphenyl maltoside.     

Diastereoselective synthesis of protected syn 1,3-diols: preparation of the C16-C24 portion of Dolabelides

We have designed a new method to make synthons encompassing a protected syn 1,3-diol motif and an aldehyde alpha to the 1,3-dioxane ring. An additional stereocenter was also created, potentially leading to stereochemically defined 1,2,4-triols. This method was successfully applied to the synthesis of the C16-C24 portion of Dolabelides.