New magnetic nano-absorbent for the determination of n-octanol/water partition coefficients

A novel and generic miniaturization methodology for the determination of partition coefficient values of organic compounds in noctanol/water by using magnetic nanoparticles is, for the first time, described. We have successfully designed, synthesised and characterised new colloidal stable porous silica-encapsulated magnetic nanoparticles of controlled dimensions. These nanoparticles absorbing a tiny amount of n-octanol in their porous silica over-layer are homogeneously dispersed into a bulk aqueous phase (pH 7.40) containing an organic compound prior to magnetic separation. The small size of the particles and the efficient mixing allow a rapid establishment of the partition equilibrium of the organic compound between the solid supported n-octanol nano-droplets and the bulk aqueous phase. UV-vis spectrophotometry is then applied as a quantitative method to determine the concentration of the organic compound in the aqueous phase both before and after partitioning (after magnetic separation). log D values of organic compounds of pharmaceutical interest (0.65-3.50), determined by this novel methodology, were found to be in excellent agreement with the values measured by the shake-flask method in two independent laboratories, which are also consistent with the literature data. It was also found that this new technique gives a number of advantages such as providing an accurate measurement of log D value, a much shorter experimental time and a smaller sample size required. With this approach, the formation of a problematic emulsion, commonly encountered in shake-flask experiments, is eliminated. It is envisaged that this method could be applicable to the high throughput log D screening of drug candidates. (c) 2005 Elsevier B.V. All rights reserved.

Monodisperse binary nanocomposite in silica with enhanced magnetization for magnetic separation

The majority of research on magnetic nanoparticles has focused on optical, electrical, and magnetic storage areas. Recently, the application of magnetic nanoparticles as magnetically separable nanovehicles for chemical or biological species has become an area of intensive research but with rather different challenging criteria that are yet to be addressed. For example, the enhancement of intrinsically weak magnetic properties, avoidance of magnetic interactions among particles, and improvement of the stability of the nanoparticles remain key issues. Here, it is demonstrated using sequential nanochemistry preparation techniques that exchange-coupled nanomagnets, such as FePt-Fe3Pt or FePt-Fe3O4 with dramatically enhanced magnetization, can be placed inside a silica nanosphere. The advantages of enhanced magnetization and the provision of protective coating and anchored sites on the silica shell surface render these new coated particles suitable for use in magnetic separation.

Solar cycle 24: implications for energetic particles and long-term space climate change

The recent solar minimum was the longest and deepest of the space age, with the lowest average sunspot numbers for nearly a century. The Sun appears to be exiting a grand solar maximum (GSM) of activity which has persisted throughout the space age, and is headed into a significantly quieter period. Indeed, initial observations of solar cycle 24 (SC24) continue to show a relatively low heliospheric magnetic field strength and sunspot number (R), despite the average latitude of sunspots and the inclination of the heliospheric current sheet showing the rise to solar maximum is well underway. We extrapolate the available SC24 observations forward in time by assuming R will continue to follow a similar form to previous cycles, despite the end of the GSM, and predict a very weak cycle 24, with R peaking at ∼65–75 around the middle/end of 2012. Similarly, we estimate the heliospheric magnetic field strength will peak around 6nT. We estimate that average galactic cosmic ray fluxes above 1GV rigidity will be ∼10% higher in SC24 than SC23 and that the probability of a large SEP event during this cycle is 0.8, compared to 0.5 for SC23. Comparison of the SC24 R estimates with previous ends of GSMs inferred from 9300 years of cosmogenic isotope data places the current evolution of the Sun and heliosphere in the lowest 5% of cases, suggesting Maunder Minimum conditions are likely within the next 40 years.

The heliospheric magnetic field

The heliospheric magnetic field (HMF) is the extension of the coronal magnetic field carried out into the solar system by the solar wind. It is the means by which the Sun interacts with planetary magnetospheres and channels charged particles propagating through the heliosphere. As the HMF remains rooted at the solar photosphere as the Sun rotates, the large-scale HMF traces out an Archimedean spiral. This pattern is distorted by the interaction of fast and slow solar wind streams, as well as the interplanetary manifestations of transient solar eruptions called coronal mass ejections. On the smaller scale, the HMF exhibits an array of waves, discontinuities, and turbulence, which give hints to the solar wind formation process. This review aims to summarise observations and theory of the small- and large-scale structure of the HMF. Solar-cycle and cycle-to-cycle evolution of the HMF is discussed in terms of recent spacecraft observations and pre-spaceage proxies for the HMF in geomagnetic and galactic cosmic ray records.

Boundary condition effects in the simulation study of equilibrium properties of magnetic dipolar fluids

In this paper we investigate the equilibrium properties of magnetic dipolar (ferro-) fluids and discuss finite-size effects originating from the use of different boundary conditions in computer simulations. Both periodic boundary conditions and a finite spherical box are studied. We demonstrate that periodic boundary conditions and subsequent use of Ewald sum to account for the long-range dipolar interactions lead to a much faster convergence (in terms of the number of investigated dipolar particles) of the magnetization curve and the initial susceptibility to their thermodynamic limits. Another unwanted effect of the simulations in a finite spherical box geometry is a considerable sensitivity to the container size. We further investigate the influence of the surface term in the Ewald sum-that is, due to the surrounding continuum with magnetic permeability mu(BC)-on the convergence properties of our observables and on the final results. The two different ways of evaluating the initial susceptibility, i.e., (1) by the magnetization response of the system to an applied field and (2) by the zero-field fluctuation of the mean-square dipole moment of the system, are compared in terms of speed and accuracy.

Structure and magnetic properties of mono- and bi-dispersed ferrofluids as revealed by simulations

Using a Langevin molecular dynamics simulation, we show that the magnetic properties of a mono- and bi-dispersed ferrofluid system depend on the volume fraction and the dipolar coupling parameter. For the bi-dispersed system, most of the chains are formed by the large particles, but the aggregation behavior of the large particles is hindered by the presence of the small particles, which are predominantly attached to the end of the particle chain. To further elucidate the microscopic fluid structure, anisotropic structure factors are calculated.

Applying the chain formation model to magnetic properties of aggregated ferrofluids

The magnetization properties of aggregated ferrofluids are calculated by combining the chain formation model developed by Zubarev with the modified mean-field theory. Using moderate assumptions for the inter- and intrachain interactions we obtain expressions for the magnetization and initial susceptibility. When comparing the results of our theory to molecular dynamics simulations of the same model we find that at large dipolar couplings (lambda>3) the chain formation model appears to give better predictions than other analytical approaches. This supports the idea that chain formation is an important structural ingredient of strongly interacting dipolar particles.

Structure and magnetic properties of polydisperse ferrofluids: a molecular dynamics study

We study by Langevin molecular dynamics simulations systematically the influence of polydispersity in the particle size, and subsequently in the dipole moment, on the physical properties of ferrofluids. The polydispersity is in a first approximation modeled by a bidisperse system that consists of small and large particles at different ratios of their volume fractions. In the first part of our investigations the total volume fraction of the system is fixed, and the volume fraction phi(L) of the large particles is varied. The initial susceptibility chi and magnetization curve of the systems show a strong dependence on the value of phi(L). With the increase of phi(L), the magnetization M of the system has a much faster increment at weak fields, and thus leads to a larger chi. We performed a cluster analysis that indicates that this is due to the aggregation of the large particles in the systems. The average size of these clusters increases with increasing phi(L). In the second part of our investigations, we fixed the volume fraction of the large particles, and increased the volume fraction phi(S) of the small particles in order to study their influence on the chain formation of the large ones. We found that the average aggregate size formed by large particles decreases when phi(S) is increased, demonstrating a significant effect of the small particles on the structural properties of the system. A topological analysis of the structure reveals that the majority of the small particles remain nonaggregated. Only a small number of them are attracted to the ends of the chains formed by large particles.

Modulation of UK lightning by heliospheric magnetic field polarity

Observational studies have reported solar magnetic modulation of terrestrial lightning on a range of time scales, from days to decades. The proposed mechanism is two-step: lightning rates vary with galactic cosmic ray (GCR) flux incident on Earth, either via changes in atmospheric conductivity and/or direct triggering of lightning. GCR flux is, in turn, primarily controlled by the heliospheric magnetic field (HMF) intensity. Consequently, global changes in lightning rates are expected. This study instead considers HMF polarity, which doesnʼt greatly affect total GCR flux. Opposing HMF polarities are, however, associated with a 40–60% difference in observed UK lightning and thunder rates. As HMF polarity skews the terrestrial magnetosphere from its nominal position, this perturbs local ionospheric potential at high latitudes and local exposure to energetic charged particles from the magnetosphere. We speculate as to the mechanism(s) by which this may, in turn, redistribute the global location and/or intensity of thunderstorm activity.

Dawn-dusk asymmetry in particles of solar wind origin within the magnetosphere

Solar wind/magnetosheath plasma in the magnetosphere can be identified using a component that has a higher charge state, lower density and, at least soon after their entry into the magnetosphere, lower energy than plasma from a terrestrial source. We survey here observations taken over 3 years of He2+ ions made by the Magnetospheric Ion Composition Sensor (MICS) of the Charge and Mass Mgnetospheric Ion Composition Experiment (CAMMICE) instrument aboard POLAR. The occurrence probability of these solar wind ions is then plotted as a function of Magnetic Local Time (MLT) and invariant latitude (3) for various energy ranges. For all energies observed by MICS (1.8–21.4 keV) and all solar wind conditions, the occurrence probabilities peaked around the cusp region and along the dawn flank. The solar wind conditions were filtered to see if this dawnward asymmetry is controlled by the Svalgaard-Mansurov effect (and so depends on the BY component of the interplanetary magnetic field, IMF) or by Fermi acceleration of He2+ at the bow shock (and so depends on the IMF ratio BX/BY ). It is shown that the asymmetry remained persistently on the dawn flank, suggesting it was not due to effects associated with direct entry into the magnetosphere. This asymmetry, with enhanced fluxes on the dawn flank, persisted for lower energy ions (below a “cross-over” energy of about 23 keV) but reversed sense to give higher fluxes on the dusk flank at higher energies. This can be explained by the competing effects of gradient/curvature drifts and the convection electric field on ions that are convecting sunward on re-closed field lines. The lower-energy He2+ ions E × B drift dawnwards as they move earthward, whereas the higher energy ions curvature/gradient drift towards dusk. The convection electric field in the tail is weaker for northward IMF. Ions then need less energy to drift to the dusk flank, so that the cross-over energy, at which the asymmetry changes sense, is reduced.

Do the legs of magnetic clouds contain twisted flux-rope magnetic fields?

Magnetic clouds (MCs) are a subset of interplanetary coronal mass ejections (ICMEs) characterised primarily by a smooth rotation in the magnetic field direction indicative of the presence of a magnetic flux rope. Energetic particle signatures suggest MC flux ropes remain magnetically connected to the Sun at both ends, leading to widely used model of global MC structure as an extended flux rope, with a loop-like axis stretching out from the Sun into the heliosphere and back to the Sun. The time of flight of energetic particles, however, suggests shorter magnetic field line lengths than such a continuous twisted flux rope would produce. In this study, two simple models are compared with observed flux rope axis orientations of 196 MCs to show that the flux rope structure is confined to the MC leading edge. The magnetic cloud “legs,” which magnetically connect the flux rope to the Sun, are not recognisable as MCs and thus are unlikely to contain twisted flux rope fields. Spacecraft encounters with these non-flux rope legs may provide an explanation for the frequent observation of non-magnetic cloud ICMEs.