Freezing of He-4 and its liquid-solid interface from Density Functional Theory

We show that, at high densities, fully variational solutions of solid-like type can be obtained from a density functional formalism originally designed for liquid 4He. Motivated by this finding, we propose an extension of the method that accurately describes the solid phase and the freezing transition of liquid 4He at zero temperature. The density profile of the interface between liquid and the (0001) surface of the 4He crystal is also investigated, and its surface energy evaluated. The interfacial tension is found to be in semiquantitative agreement with experiments and with other microscopic calculations. This opens the possibility to use unbiased DF methods to study highly non-homogeneous systems, like 4He interacting with strongly attractive impurities/substrates, or the nucleation of the solid phase in the metastable liquid.Comment: 5 pages, 4 figures, submitted to Phys. Rev.

Charge Renormalization, Effective Interactions, and Thermodynamics of Deionized Colloidal Suspensions

Thermodynamic properties of charge-stabilised colloidal suspensions depend sensitively on the effective charge of the macroions, which can be substantially lower than the bare charge in the case of strong counterion-macroion association. A theory of charge renormalization is proposed, combining an effective one-component model of charged colloids with a thermal criterion for distinguishing between free and associated counterions. The theory predicts, with minimal computational effort, osmotic pressures of deionized suspensions of highly charged colloids in close agreement with large-scale simulations of the primitive model.Comment: 15 pages, 7 figure

Poisson-Boltzmann Theory of Charged Colloids: Limits of the Cell Model for Salty Suspensions

Thermodynamic properties of charge-stabilised colloidal suspensions are commonly modeled by implementing the mean-field Poisson-Boltzmann (PB) theory within a cell model. This approach models a bulk system by a single macroion, together with counterions and salt ions, confined to a symmetrically shaped, electroneutral cell. While easing solution of the nonlinear PB equation, the cell model neglects microion-induced correlations between macroions, precluding modeling of macroion ordering phenomena. An alternative approach, avoiding artificial constraints of cell geometry, maps a macroion-microion mixture onto a one-component model of pseudo-macroions governed by effective interactions. In practice, effective-interaction models are usually based on linear screening approximations, which can accurately describe nonlinear screening only by incorporating an effective (renormalized) macroion charge. Combining charge renormalization and linearized PB theories, in both the cell model and an effective-interaction (cell-free) model, we compute osmotic pressures of highly charged colloids and monovalent microions over a range of concentrations. By comparing predictions with primitive model simulation data for salt-free suspensions, and with predictions of nonlinear PB theory for salty suspensions, we chart the limits of both the cell model and linear-screening approximations in modeling bulk thermodynamic properties. Up to moderately strong electrostatic couplings, the cell model proves accurate in predicting osmotic pressures of deionized suspensions. With increasing salt concentration, however, the relative contribution of macroion interactions grows, leading predictions of the cell and effective-interaction models to deviate. No evidence is found for a liquid-vapour phase instability driven by monovalent microions. These results may guide applications of PB theory to soft materials.Comment: 27 pages, 5 figures, special issue of Journal of Physics: Condensed Matter on "Classical density functional theory methods in soft and hard matter

The catalytic Mitsunobu reaction: a critical analysis of the current state-of-the-art

The Mitsunobu reaction is widely regarded as the pre-eminent method for performing nucleophilic substitutions of alcohols with inversion of configuration. However, its applicability to large-scale synthesis is undermined by the fact that alcohol activation occurs at the expense of two stoichiometric reagents – a phosphine and an azodicarboxylate. The ideal Mitsunobu reaction would be sub-stoichiometric in the phosphine and azodicarboxylate species and employ innocuous terminal oxidants and reductants to achieve recycling. This Review article provides a summary and analysis of recent advances towards the development of such catalytic Mitsunobu reactions

Field line distribution of density at \u3ci\u3eL\u3c/i\u3e=4.8 inferred from observations by CLUSTER

For two events observed by the CLUSTER space- craft, the field line distribution of mass density ρ was inferred from Alfve ́n wave harmonic frequencies and compared to the electron density ne from plasma wave data and the oxy- gen density nO+ from the ion composition experiment. In one case, the average ion mass M≡ρ/ne was about 5amu (28 October 2002), while in the other it was about 3 amu (10 September 2002). Both events occurred when the CLUSTER 1 (C1) spacecraft was in the plasmatrough. Nevertheless, the electron density ne was significantly lower for the first event (ne =8 cm−3 ) than for the second event (ne =22 cm−3 ), and this seems to be the main difference leading to a dif- ferent value of M. For the first event (28 October 2002), we were able to measure the Alfve ́n wave frequencies for eight harmonics with unprecedented precision, so that the er- ror in the inferred mass density is probably dominated by factors other than the uncertainty in frequency (e.g., mag- netic field model and theoretical wave equation). This field line distribution (at L=4.8) was very flat for magnetic lati- tude |MLAT|20◦ but very steeply increasing with respect to |MLAT| for |MLAT|40◦. The total variation in ρ was about four orders of magnitude, with values at large |MLAT| roughly consistent with ionospheric values. For the second event (10 September 2002), there was a small local maxi- mum in mass density near the magnetic equator. The in- ferred mass density decreases to a minimum 23% lower than the equatorial value at |MLAT|=15.5◦, and then steeply in- creases as one moves along the field line toward the iono- sphere. For this event we were also able to examine the spa- tial dependence of the electron density using measurements of ne from all four CLUSTER spacecraft. Our analysis in- dicates that the density varies with L at L∼5 roughly like L−4, and that ne is also locally peaked at the magnetic equa- tor, but with a smaller peak. The value of ne reaches a den- sity minimum about 6% lower than the equatorial value at |MLAT|=12.5◦, and then increases steeply at larger values of |MLAT|. This is to our knowledge the first evidence for a local peak in bulk electron density at the magnetic equa- tor. Our results show that magnetoseismology can be a useful technique to determine the field line distribution of the mass density for CLUSTER at perigee and that the distribution of electron density can also be inferred from measurements by multiple spacecraft

The Effect of Sub-MIC β-Lactam Antibiotic Exposure of Pseudomonas aeruginosa Strains from People with Cystic Fibrosis in a Desiccation Survival Model

Prior to modern typing methods, cross-infection of P. aeruginosa between people with cystic fibrosis (CF) was felt to be rare. Recently a number of studies have demonstrated the presence of clonal strains of P. aeruginosa infecting people with CF. The aim of this study was to determine whether strains of P. aeruginosa demonstrated differences in resistance to desiccation and whether preincubation in subminimum inhibitory concentrations (MICs) of β-lactam affected desiccation resistance. The experimental data were modelled to a first-order decay model and a Weibull decay model using least squares nonlinear regression. The Weibull model was the preferred model for the desiccation survival. The presence of a mucoid phenotype promoted desiccation survival. Preincubation with antibiotics did not have a consistent effect on the strains of P. aeruginosa. Meropenem reduced desiccation resistance, whereas ceftazidime had much less effect on the strains studied