In Defense of Vapor Pressure Osmometry for Measuring Molecular Weight

The value of the average molecular weight of petroleum asphaltenes continues to be controversial. Usually the disagreement is about the measurement of a single asphaltene fraction when the need is for a consistent picture that comprises all fractions of petroleum and includes chemical changes during processing. By using one of the better solvents for carbonaceous materials, o‐dichlorobenzene, at the maximum instrument temperature, vapor pressure osmometry provides a consistent measurement of number average molecular weight not achieved by any other technique. This average molecular weight is consistent among petroleum fractions and gives predictable changes in asphaltene molecular weight with thermal processing.     

Cranberry derived proanthocyanidins reduce bacterial adhesion to selected biomaterials

Catheter associated urinary tract infections (CAUTI) linked with the uropathogens Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) account for the majority of nosocomial infections acquired in the clinical environment. Because these infections develop following initial adhesion of the bacterial pathogens to the catheter surface, there is increased interest in developing effective methods to inhibit attachment of cells to biomaterials used in the manufacture of indwelling devices. High molecular weight proanthocyanidins (PAC) extracted from the North American cranberry (Vaccinium macrocarpon) were examined for their potential to reduce the initial adhesion of uropathogenic bacteria (E. coli CFT073 and E. faecalis 29212) to two model biomaterials, poly(vinyl chloride) (PVC) and polytetrafluoroethylene (PTFE). Well-controlled experiments conducted in a parallel-plate flow chamber (PPFC) demonstrated decreased attachment of both bacteria to PVC and PTFE when either the bacteria, biomaterial or both surfaces were treated with PAC. Most significant inhibition of bacterial adhesion was observed for the condition where both the bacteria and biomaterial surfaces were coated with PAC. Additional experiments conducted with nonbiological model particles demonstrate comparable extents of adhesion inhibition, supporting a nonbiospecific mechanism of PAC action. The results of this study are promising for the implementation of PAC in the clinical milieu for prevention of device associated infection as the proposed functional modification is independent of antibacterial mechanisms that may give rise to resistant strains.     

Ab initio study of substituent effects in the interactions of dimethyl ether with aromatic rings

Ab initio calculations have been used to investigate the interaction energies of dimers of dimethyl ether with benzene, hexafluorobenzene, and several monosubstituted benzenes. The potential energy curves were explored at the MP2/aug-cc-pVDZ level for two basic configurations of the dimers, one in which the oxygen atom of the dimethyl ether was pointed towards the aromatic ring and the other in which the oxygen atom was pointed away from the aromatic ring. Once the optimum intermolecular distances between the dimethyl and the aromatic ring had been determined for each of the dimers in both configurations at the MP2/aug-cc-pVDZ level, single point energy calculations were performed at the MP2/aug-cc-pVTZ level. A CCSD(T) correction term to the energy was determined and this was combined with the MP2/aug-cc-pVTZ energies to estimate the CCSD(T)/aug-cc-pVTZ interaction energies of the dimers. The estimated CCSD(T)/aug-cc-pVTZ interaction energies are predicted to be attractive for all of the dimers in both configurations and dispersion interactions are found to be a large component of the stabilization of the dimers. For the dimers with the dimethyl ether oxygen pointing towards the aromatic ring, the strengths of interaction energies are found to increase as the aromatic ring becomes more electron deficient, while for the dimers with the dimethyl ether oxygen pointing away from the aromatic ring, they increase as the aromatic ring becomes more electron rich. In both cases, the trends can be explained in terms of the electrostatic potentials of the dimethyl ether and the aromatic rings.     

Darwinian Docking

The Darwinian model of evolution is an optimization strategy that can be adapted to docking. It differs from the common use of genetic algorithms, primarily in its acceptance of diverse solutions over finding "global" optima. A related problem is selecting compounds using multiple criteria. I discuss these ideas and present the outlines of a protocol for selecting "hits" and "leads" in drug discovery.     

Projective Fraïssé limits and the pseudo-arc

The aim of the present work is to develop a dualization of the Fraïssé limit construction from model theory and to indicate its surprising connections with the pseudo-arc. As corollaries of general results on the dual Fraïssé limits, we obtain Mioduszewski's theorem on surjective universality of the pseudo-arc among chainable continua and a theorem on projective homogeneity of the pseudo-arc (which generalizes a result of Lewis and Smith on density of homeomorphisms of the pseudo-arc among surjective continuous maps from the pseudo-arc to itself). We also get a new characterization of the pseudo-arc via the projective homogeneity property.

     

Regularized state-constrained boundary optimal control of the Navier-Stokes equations

The numerical solution of the Dirichlet boundary optimal control problem of the Navier-Stokes equations in presence of pointwise state constraints is investigated. Two different regularization techniques are considered. First, a Moreau-Yosida regularization of the problem is studied. Optimality conditions are derived and the convergence of the regularized solutions towards the original one is proved. A source representation of the control combined with a Lavrentiev type regularization strategy is also presented. The analysis concerning optimality conditions and convergence of the regularized solutions is carried out. In the last part of the paper numerical experiments are presented. For the numerical solution of each regularized problem a semi-smooth Newton method is applied.     

Investigation of new band parameters with temperature dependence for self-broadened methane gas in the range 9000 to 14,000 cm−1 (0.71 to 1.1 μm)

This paper describes new measurements and modelling of the absorption of methane gas, one of the most important gases observed in the atmospheres of the outer planets and Titan, between 9000 and 14,000 cm^?1 (0.7 to 1.1 μm) and compares them with current best available spectral models.A series of methane spectra were measured at the UK's Natural Environment Research Council (NERC) Molecular Spectroscopy Facility (based at the Rutherford Appleton Laboratory, Oxfordshire, UK) using a Brüker 125HR Fourier transform spectrometer. To approximate the conditions found in outer planet atmospheres, the spectra were measured over a wide range of pressures (5 bar to 38 mbar) and temperatures (290–100 K) with path lengths of 19.3, 17.6, 16.0 and 14.4 m. The spectra were recorded at a moderate resolution of 0.12 cm^?1 and then averaged to 10 cm^?1 resolution prior to fitting a series of increasingly complex band-models including temperature dependence. Using the most complex model, a Goody line distribution with a Voigt line shape and two lower energy state levels, the typical rms residual error in the fit is between 0.01 and 0.02 in the wings of the main absorption bands.The new spectral parameters were then compared with the measured spectra and spectra calculated using existing data and shown to be able to accurately reproduce the measured absorption. The improvement in the temperature dependence included in the model is demonstrated by comparison with existing cold methane spectral data for a typical Jovian path.     

Task Specific and General Patterns of Joint Motion Variability in Upright- and Hand-Standing Postures

The preservation of static balance in both upright- and hand-stance is maintained by the projection of center of mass (CM) motion within the region of stability at the respective base of support. This study investigated, from a degrees of freedom (DF) perspective, whether the stability of the CM in both upright- and hand-stances was predicted by the respective dispersion and time-dependent regularity of joint (upright stance—ankle, knee, hip, shoulder, neck; hand stance—wrist, elbow, shoulder, neck) angle and position. Full body three-dimensional (3D) kinematic data were collected on 10 advanced level junior female gymnasts during 30 s floor upright- and hand-stands. For both stances the amount of the dispersion of joint angle and sway motion was higher than that of the CM and center of pressure (CP) with an inverse relation to time-dependent irregularity (SampEn). In upright-standing the variability of neck motion in the anterior–posterior direction was significantly greater than that of most joints consistent with the role of vision in the control of quiet upright posture. The findings support the proposition that there are both task specific and general properties to the global CM control strategy in the balance of upright- and hand-standing induced by the different active skeletal-muscular organization and the degeneracy revealed in the multiple distributional variability patterns of the joint angle and position in 3D.