Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.     

Steric Effects Govern the Photoactivation of Phytochromes

Phytochromes constitute a superfamily of photoreceptor proteins existing in two forms that absorb red (Pr) and far‐red (Pfr) light. Although it is well‐known that the conversion of Pr into Pfr (the biologically active form) is triggered by a Z→E photoisomerization of the linear tetrapyrrole chromophore, direct evidence is scarce as to why this reaction always occurs at the methine bridge between pyrrole rings C and D. Here, we present hybrid quantum mechanics/molecular mechanics calculations based on a high‐resolution Pr crystal structure of Deinococcus radiodurans bacteriophytochrome to investigate the competition between all possible photoisomerizations at the three different (AB, BC and CD) methine bridges. The results demonstrate that steric interactions with the protein are a key discriminator between the different reaction channels. In particular, it is found that such interactions render photoisomerizations at the AB and BC bridges much less probable than photoisomerization at the CD bridge.     

Read and write processes, and head technology for perpendicular recording

In this paper, we present a review of the write and read processes in perpendicular magnetic recording. We also discuss their impact, based on recording physics aspects, on design considerations for writers and readers. For the write process, we discuss fundamental write-ability limitations as well as possible paths to ultra-high areal density perpendicular recording. The impacts of different medium designs, geometrical scaling, and the breakdown of scaling, both in terms of write-ability and transition curvature, are shown based on different modeling techniques, including analytical formulas, finite element modeling (FEM), and micromagnetic simulations. Basic design rules as well as alternative designs that enable high areal density are briefly explained. For the read-back process, the relation between reader signal to noise ratio (SNR) and resistance, as well as reader resistance shunt and spacing loss, are discussed. Finally, we use a simple example to illustrate, both from a write as well as a read-back perspective, the complicated nature of perpendicular recording systems, and how different medium designs impact recording head technology for ultra high density perpendicular recording.     

Biased random walk in a one-dimensional percolation model

We consider random walk with a nonzero bias to the right, on the infinite cluster in the following percolation model: take i.i.d. bond percolation with retention parameter p$p$ on the so-called infinite ladder, and condition on the event of having a bi-infinite path from −∞$-\infty$ to ∞$\infty$. The random walk is shown to be transient, and to have an asymptotic speed to the right which is strictly positive or zero depending on whether the bias is below or above a certain critical value which we compute explicitly.     

Ion-pair supercritical fluid chromatography of metoprolol and related amino alcohols on diol silica

In this paper, a chromatographic system based on carbon dioxide with methanol as mobile phase, and diol silica as stationary phase has been investigated for metoprolol and related amino alcohols by addition of strong acids to systems with triethylamine base as primary additive. Standard conditions used were 10% of methanol, containing 24 mM of acid and 18 mM of triethylamine, in carbon dioxide with a flow rate of 1.5 ml min(-1). The column dimensions were 125 mm x 4 mm I.D. and kept at 40 degrees C with a back pressure of 150 bar. Effects on selectivity were stronger with trifluoroacetic acid than with ethanesulfonic acid. From a large set of related analytes, it was shown that selectivity changes were significant when the structure close to the nitrogen of the amino alcohol analyte differed. The stability of the column in the short time perspective was examined and it showed negligible changes. For a diastereoisomeric pair, not resolved in a basic system with triethylamine nor by addition of ethanesulfonic acid, resolution improved to about 2.1 with trifluoroacetic acid. The described approach offers a way to tune the selectivity of SFC systems when amines are analyzed without the need to change stationary phase for the chromatographic separation.     

Mapping the intracellular fraction of water by varying the gradient pulse length in q-space diffusion MRI

Finite gradient pulse lengths are traditionally considered a nuisance in q-space diffusion NMR and MRI, since the simple Fourier relation between the acquired signal and the displacement probability is invalidated. Increasing the value of the pulse length leads to an apparently smaller value of the estimated compartment size. We propose that q-space data at different gradient pulse lengths, but with the same effective diffusion time, can be used to identify and quantify components with free or restricted diffusion from multiexponential echo decay curves obtained on cellular systems. The method is demonstrated with experiments on excised human brain white matter and a series of model systems with well-defined free, restricted, and combined free and restricted diffusion behavior. Time-resolved diffusion MRI experiments are used to map the spatial distribution of the intracellular fraction in a yeast cell suspension during sedimentation, and observe the disappearance of this fraction after a heat treatment.     

First principles calculations of magnetism, dielectric properties and spin-phonon coupling in double perovskite Bi(2)CoMnO(6)

First principles electronic structure calculations have been performed for the double perovskite Bi(2)CoMnO(6) in its non-centrosymmetric polar state using the generalized gradient approximation plus the Hubbard U approach. We find that the ferromagnetic state is more favored compared to the ferrimagnetic state with both Co and Mn in high spin states. The calculated dynamical charge tensors are anisotropic reflecting a low-symmetry structure of the compound. The magnetic structure dependent phonon frequencies indicate the presence of a weak spin-phonon coupling. Using the Berry phase method, we obtain a spontaneous ferroelectric polarization of 5.88?μC?cm(-2), which is close to the experimental value observed for a similar compound, Bi(2)NiMnO(6).     

A chemically sterilizable barrier for the protection of fermentors during automatic sampling into a low-injection system

Two three-way valves are connected by a short stainless steel tube and attached to a model fermentor. A sample can be drawn straight through the valves and into an analyzer for monitoring of oxygen or glucose. The valves are switched to an external solution after the sample has been taken. Solutions of 5% formaldehyde provide a barrier to the intrusion of micro-organisms into the fermentor, whereas water solutions are ineffective. With water in the barrier, infections occur after a few days when the system is provoked by a growing culture ofE.coli at the outlet. The concept of a chemically sterilizable barrier is particularly well suited for the intermittent needs of flow-injection systems used for process monitoring.