Marine biological reference materials for methylmercury: analytical methodologies used in certification

Summary The methylmercury concentrations in three existing marine biological certified reference materials — TORT-1, DORM-1 and DOLT-1 — are determined by gas chromatography with electron capture detection, cold vapour atomic absorption spectrometry and inductively coupled plasma mass spectrometry after selective isolation of methylmercury. Two such procedures were used. These and the three analytical techniques are evaluated and compared. The certified methylmercury concentrations are: TORT-1, 0.128 ± 0.014; DORM-1, 0.731±0.060; and DOLT-1, 0.080 ± 0.011 g Hg/g dry weight.

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Meeresbioligische Referenzmaterialien für Methylquecksilber: Analytische Methoden der Zertifizierung

     

Application of accelerated molecular dynamics schemes to the production of amorphous silicon

The evolving nature of a Stillinger-Weber modeled silicon glass is studied using two accelerated molecular dynamics scheme, specifically, hyperdynamics and self-guided algorithms due to Voter and due to Wu and Wang, respectively. We obtain an acceleration of the dynamics, a "boost," on the order of 20 without incurring any significant computational overhead. The validity of the results using accelerated methods is provided by comparison to a conventional molecular dynamics (MD) algorithm simulated under constant temperature conditions for more than 100 ns. We found that performing a sensitivity analysis of the effect of the parameters lambda and t1 before applying the self-guided MD scheme was important. Values of lambda greater than 0.1 and t1 equal to 1 ps were found to give improved structural evolution as compared to a conventional MD scheme. The hyperdynamics approximation scheme was found to be effective in obtaining boosts in the range of 4-12 for a small system without changing the dynamics of the evolution. However, for a large system size such an approach introduces significant perturbations to the pertinent equations of motion.     

Trapping dynamics of diindenoperylene (DIP) in self-assembled monolayers using molecular simulation

All-atom Molecular Dynamics simulation methods employing a well-tested intermolecular potential model, MM3 (Molecular Mechanics 3), demonstrate the propensity for diindenoperylene (DIP) molecules to insert between molecules of a self-assembled monolayer (SAM) during a deposition process intended to grow a thin film of this organic semiconductor molecule onto the surface of self-assembled monolayers. The tendency to insert between SAM molecules is fairly prevalent at normal growth temperatures and conditions, but is most strongly dependent on the density and the nature of the SAM. We posit the existence of an optimal density to favor surface adsorption over insertion for this system. DIP is less likely to insert in fluorinated SAMs, like FOTS (fluorooctatrichlorosilane), than its unfluorinated analog, OTS (octatrichlorosilane). It is also less likely to insert between shorter SAMs (e.g., less insertion in OTS than ODTS (octadecyltrichlorosilane)). Very short length, surface-coating molecules, like HDMS (hexamethyldisilazane), are more likely to scatter energetic incoming DIP molecules with little insertion on first impact (depending on the incident energy of the DIP molecule). Grazing angles of incidence of the depositing molecules generally favor surface adsorption, at least in the limit of low coverage, but are shown to be dependent on the nature of the SAM. The validity of these predictions is confirmed by comparison of the predicted sticking coefficients of DIP at a variety of incident energies on OTS, ODTS, and FOTS SAMs with results obtained experimentally by Desai et al. (2010) [23]. The simulation predictions of the tendency of DIP to insert can be explained, in large part, in terms of binding energies between SAM and DIP molecules. However, we note that entropic and stochastic events play a role in the deposition outcomes. Preliminary studies of multiple deposition events, emulating growth, show an unexpected diffusion of DIP molecules inserted within the SAM matrix in a clear attempt of the DIP molecules to aggregate together.     

Observation of nearly perfect irrotational flow in normal and superfluid strongly interacting Fermi gases

We study the hydrodynamic expansion of a rotating strongly interacting Fermi gas by releasing a cigar-shaped cloud with a known angular momentum from an optical trap. As the aspect ratio of the expanding cloud approaches unity, the angular velocity increases, indicating quenching of the moment of inertia I to as low as 0.05 of the rigid body value I(rig). Remarkably, we observe this behavior in both the superfluid and collisional normal fluid regimes, which obey nearly identical zero-viscosity irrotational hydrodynamics. We attribute irrotational flow in the normal fluid to a decay of the rotational part of the stream velocity during expansion, which occurs when the shear viscosity is negligible. Using conservation of angular momentum, we directly observe a fundamental result of irrotational hydrodynamics, I/I(rig) = delta2, where delta is the deformation parameter of the cloud.     

Intermolecular potential energy functions from gaseous viscosity data. Choice of the well depth

Dilute gas viscosity data may be inverted directly to give the intermolecular potential energy function if the well depth is known. The consequences of using different values of the well depth are studied, and it is concluded that the correct value may be distinguished by using second virial coefficient data.     

Approximating Time to Extinction for Endemic Infection Models

Approximating the time to extinction of infection is an important problem in infection modelling. A variety of different approaches have been proposed in the literature. We study the performance of a number of such methods, and characterise their performance in terms of simplicity, accuracy, and generality. To this end, we consider first the classic stochastic susceptible-infected-susceptible (SIS) model, and then a multi-dimensional generalisation of this which allows for Erlang distributed infectious periods. We find that (i) for a below-threshold infection initiated by a small number of infected individuals, approximation via a linear branching process works well; (ii) for an above-threshold infection initiated at endemic equilibrium, methods from Hamiltonian statistical mechanics yield correct asymptotic behaviour as population size becomes large; (iii) the widely-used Ornstein-Uhlenbeck diffusion approximation gives a very poor approximation, but may retain some value for qualitative comparisons in certain cases; (iv) a more detailed diffusion approximation can give good numerical approximation in certain circumstances, but does not provide correct large population asymptotic behaviour, and cannot be relied upon without some form of external validation (eg simulation studies).