Temperature-Dependent Diffusion Coefficients from 1D Raman Spectroscopy

A setup for the measurement of temperature-dependent diffusion coefficients has been developed based on 1D Raman spectroscopy. The presented setup was used to measure binary diffusion coefficients for mixtures of monoethanolamine + water, cyclohexane + toluene, and methanol + toluene for temperatures between T = 298.15 and 330.15 K. The experimental diffusion coefficients agree well with available literature data. For the mixture methanol + toluene, literature data was only found for T = 298.15 K. The novel setup was therefore used to determine temperature-dependent diffusion coefficients of methanol + toluene up to T = 328.15 K. The experimental data are also compared to a temperature correlation for diffusion coefficients in concentrated solutions. While the correlation describes the temperature dependence well for simple systems, measurement techniques remain indispensable for diffusion in complex mixtures.     

Protein Denaturation Through the Use of Magnetic Molecularly Imprinted Polymer Nanoparticles

The inhibition of the protein function for therapeutic applications remains challenging despite progress these past years. While the targeting application of molecularly imprinted polymer are in their infancy, no use was ever made of their magnetic hyperthermia properties to damage proteins when they are coupled to magnetic nanoparticles. Therefore, we have developed a facile and effective method to synthesize magnetic molecularly imprinted polymer nanoparticles using the green fluorescent protein (GFP) as the template, a bulk imprinting of proteins combined with a grafting approach onto maghemite nanoparticles. The hybrid material exhibits very high adsorption capacities and very strong affinity constants towards GFP. We show that the heat generated locally upon alternative magnetic field is responsible of the decrease of fluorescence intensity.     

On 3-braids and L-space knots

Geometriae Dedicata - We classify closed 3-braids which are L-space knots.     

“Beyond an acronym,STEM is…”: Perceptions of STEM

Although STEM is at the forefront of many educational initiatives, little is known about various professionals’ perceptions of STEM. This mixed‐methods study surveyed 164 preservice teachers, inservice teachers, administrators, informal educators, and STEM professionals. Quantitative and qualitative questions on the survey elicited participants’ perceptions of STEM, STEM support, and STEM careers. Quantitative analysis revealed that profession influenced understandings of STEM, importance of STEM, support for STEM, and perceptions of STEM career opportunities. Qualitative analysis provided rich explanations for the differences in perceptions among professions. This study suggests that science teacher educators need to ensure preservice teachers have understandings of STEM and STEM careers, K‐16 educators need to emphasize the current importance of STEM, and administrators and policymakers need to align visions of STEM with curriculum and pacing guides so teachers feel supported in their STEM endeavors.     

Analysis of the collective behavior of a 10 by 10 array of Fe3O4 dots in a large micromagnetic simulation

We report a full (3D) micromagnetic simulation of a set of 100 ferrite (Fe₃O₄) cylindrical dots, arranged in a 10 by 10 square (planar) array of side , excited by an external in-plane magnetic field. The resulting power spectrum of magnetic excitations and the dynamical magnetization field at the resulting resonance modes were investigated. The absorption spectrum deviates considerably from that of a single particle reference simulation, presenting a mode-shifting and splitting effect. We found an inversion symmetry through the center of the array, in the sense that each particle and its inversion counterpart share approximately the same magnetization mode behavior. Magnonic designs aiming at synchronous or coherent tunings of spin-wave excitations at given spatially separated points within a regular square array may benefit from the new effects here described.     

The benefit of data-based model complexity selection via prediction error curves in time-to-event data

The fitting of predictive survival models usually involves determination of model complexity parameters. Up to now, there was no general applicable model selection criterion for semi- or non-parametric approaches. The integrated prediction error curve, an estimator of the integrated Brier score, has the ability to close this gap and allows a reasonable, data-based choice of complexity parameters for any kind of model where risk predictions can be obtained. Random survival forests are used as example throughout the article. Here, a critical complexity parameter might be the number of candidate variables at each node. Model selection by our integrated prediction error curve criterion is compared to a frequently used rule of thumb, investigating the potential benefit regarding prediction performance. For that, simulated microarray survival data as well as two real data sets of patients with diffuse large-B-cell lymphoma and of patients with neuroblastoma are used. It is shown, that the optimal parameter value depends on the amount of information in the data and that a data-based selection can therefore be beneficial in several settings.     

Determination of the Avogadro constant by counting the atoms in a 28Si crystal

The Avogadro constant links the atomic and the macroscopic properties of matter. Since the molar Planck constant is well known via the measurement of the Rydberg constant, it is also closely related to the Planck constant. In addition, its accurate determination is of paramount importance for a definition of the kilogram in terms of a fundamental constant. We describe a new approach for its determination by counting the atoms in 1 kg single-crystal spheres, which are highly enriched with the 28Si isotope. It enabled isotope dilution mass spectroscopy to determine the molar mass of the silicon crystal with unprecedented accuracy. The value obtained, NA = 6.022,140,78(18) × 10(23) mol(-1), is the most accurate input datum for a new definition of the kilogram.     

Photon propagation in a discrete fiber network: an interplay of coherence and losses

We study light propagation in a photonic system that shows stepwise evolution in a discretized environment. It resembles a discrete-time version of photonic waveguide arrays or quantum walks. By introducing controlled photon losses to our experimental setup, we observe unexpected effects like subexponential energy decay and formation of complex fractal patterns. This demonstrates that the interplay of linear losses, discreteness and energy gradients leads to genuinely new coherent phenomena in classical and quantum optical experiments. Moreover, the influence of decoherence is investigated.     

Green proteorhodopsin reconstituted into nanoscale phospholipid bilayers (nanodiscs) as photoactive monomers

Over 4000 putative proteorhodopsins (PRs) have been identified throughout the oceans and seas of the Earth. The first of these eubacterial rhodopsins was discovered in 2000 and has expanded the family of microbial proton pumps to all three domains of life. With photophysical properties similar to those of bacteriorhodopsin, an archaeal proton pump, PRs are also generating interest for their potential use in various photonic applications. We perform here the first reconstitution of the minimal photoactive PR structure into nanoscale phospholipid bilayers (nanodiscs) to better understand how protein-protein and protein-lipid interactions influence the photophysical properties of PR. Spectral (steady-state and time-resolved UV-visible spectroscopy) and physical (size-exclusion chromatography and electron microscopy) characterization of these complexes confirms the preparation of a photoactive PR monomer within nanodiscs. Specifically, when embedded within a nanodisc, monomeric PR exhibits a titratable pK(a) (6.5-7.1) and photocycle lifetime (～100-200 ms) that are comparable to the detergent-solubilized protein. These ndPRs also produce a photoactive blue-shifted absorbance, centered at 377 or 416 nm, that indicates that protein-protein interactions from a PR oligomer are required for a fast photocycle. Moreover, we demonstrate how these model membrane systems allow modulation of the PR photocycle by variation of the discoidal diameter (i.e., 10 or 12 nm), bilayer thickness (i.e., 23 or 26.5 ?), and degree of saturation of the lipid acyl chain. Nanodiscs also offer a highly stable environment of relevance to potential device applications.     

Dual lithium insertion and conversion mechanisms in a titanium-based mixed-anion nanocomposite

The electrochemical reaction of lithium with a vacancy-containing titanium hydroxyfluoride was studied. On the basis of pair distribution function analysis, NMR, and X-ray photoelectron spectroscopy, we propose that the material undergoes partitioning upon initial discharge to form a nanostructured composite containing crystalline Li(x)TiO(2), surrounded by a Ti(0) and LiF layer. The Ti(0) is reoxidized upon reversible charging to an amorphous TiF(3) phase via a conversion reaction. The crystalline Li(x)TiO(2) is involved in an insertion reaction. The resulting composite electrode, Ti(0)-LiF/Li(x)TiO(2) ? TiF(3)/ Li(y)TiO(2), allows reaction of more than one Li per Ti, providing a route to higher capacities while improving the energy efficiency compared to pure conversion chemistries.