Silver Coated Platinum Core–Shell Nanostructures on Etched Si Nanowires: Atomic Layer Deposition (ALD) Processing and Application in SERS

A new method to prepare plasmonically active noble metal nanostructures on large surface area silicon nanowires (SiNWs) mediated by atomic layer deposition (ALD) technology has successfully been demonstrated for applications of surface‐enhanced Raman spectroscopy (SERS)‐based sensing. As host material for the plasmonically active nanostructures we use dense single‐crystalline SiNWs with diameters of less than 100 nm as obtained by a wet chemical etching method based on silver nitrate and hydrofluoric acid solutions. The SERS active metal nanoparticles/islands are made from silver (Ag) shells as deposited by autometallography on the core nanoislands made from platinum (Pt) that can easily be deposited by ALD in the form of nanoislands covering the SiNW surfaces in a controlled way. The density of the plasmonically inactive Pt islands as well as the thickness of noble metal Ag shell are two key factors determining the magnitude of the SERS signal enhancement and sensitivity of detection. The optimized Ag coated Pt islands on SiNWs exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability and reproducibility. The plasmonic activity of the core‐shell Pt//Ag system that will be experimentally realized in this paper as an example was demonstrated in numerical finite element simulations as well as experimentally in Raman measurements of SERS activity of a highly diluted model dye molecule. The morphology and structure of the core‐shell Pt//Ag nanoparticles on SiNW surfaces were investigated by scanning‐ and transmission electron microscopy. Optimized core–shell nanoparticle geometries for maximum Raman signal enhancement is discussed essentially based on the finite element modeling.     

Separation of amino alcohols using divalent dipeptides as counter ions in aqueous CE

Divalent dipeptides have been introduced as counter ions in aqueous CZE. The dipeptides form ion pairs with amino alcohols in the BGE and facilitate the separation of amino alcohols. High concentrations of dipeptide caused reversed effective mobility for the analytes. The net charge of the dipeptide can be controlled using a buffer or a strong base, and regulates the interaction between the dipeptide and the amino alcohol. A stronger interaction and higher selectivity of amino alcohols was observed when the dipeptides were used as divalent counter ions, than in monovalent or uncharged form. Association constants for ion pairs between divalent dipeptides and amino alcohols can be used to enhance selectivity for amino alcohols in CZE. No chiral separation of amino alcohols was observed when using the dipeptides as ion‐pairing chiral selectors in aqueous BGE, but addition of methanol to the BGE promoted enantioselectivity.     

A concise and convergent synthesis of PA-824

An efficient four-step synthesis of PA-824, a promising antituberculosis drug candidate, has been developed. This concise approach offers significant improvements over the synthetic route currently used for large-scale production.     

Synthesis and Self‐Aggregation of Enantiopure and Racemic Molecular Tweezers Based on the Bicyclo[3.3.1]nonane Framework

A pair of molecular tweezers (syn‐ 4 ) that consists of quinoline and pyrazine units fused to a bicyclic framework is presented. The tweezers were synthesised both as a racemic mixture (rac‐ 4 ) and an enantiomerically pure form ((R,R,R,R)‐ 4 ) starting from either racemic or enantiomerically pure bicyclo[3.3.1]nonane‐2,6‐dione ( 3 ). Homochiral dimers were observed in the solid state for rac‐ 4 . The self‐association of both rac‐ 4 and (R,R,R,R)‐ 4 was studied in solution. A weak self‐association constant in CDCl₃ was estimated by ¹H NMR spectroscopic dilution titration experiments in both cases, following several proton resonances. For this purpose, a general normalisation model for the accurate determination of association constants from multiple datasets was developed. In contrast to the solid state, no diastereomeric discrimination was observed for rac‐ 4 in solution.     

Mobile phase selection for the combined use of liquid chromatography–inductively coupled plasma mass spectrometry and electrospray ionisation mass spectrometry

Four different organic solvents: dimethylformamide, 1,4-dioxane, n-propanol and ethanol were evaluated as alternative organic modifiers to acetonitrile for liquid chromatography (LC) separations. The aim was to establish common sets of chromatographic conditions that could be applied for LC hyphenation to inductively coupled plasma mass spectrometry (ICPMS) as well as to electrospray ionization MS (ESIMS). The approach was to evaluate candidate solvents that, compared to acetonitrile, potentially could give improved analytical performance (low solvent vapor loading, maximized analyte sensitivity and minimized carbon depositions on instrumental parts) in ICPMS analysis while retaining chromatographic and ESIMS performances. The study showed that dimethylformamide, 1,4-dioxane, n-propanol and ethanol all can be advantageous chromatographic modifiers for LC–ICPMS analysis, giving superior performance compared to acetonitrile. For the combined use of LC–ICPMS and LC–ESIMS with a common set of chromatographic conditions, n-propanol gave the best overall performance. The ¹⁹⁵Pt⁺ signal in ICPMS was continuously monitored during a 0–60% organic solvent gradient and at 25% of organic modifier, 100% of the signal obtained at the gradient start was preserved for n-propanol compared to only 35% of the signal when using acetonitrile. Platinum detection limits were 5–8 times lower using n-propanol compared with acetonitrile. Signal-to-noise ratio in continuous ESIMS signal measurements was 100, 90 and 110 for a 100 μg/ml solution of leucine–enkephaline using acetonitrile, ethanol and n-propanol, respectively. Chromatographic efficiency in reversed phase separations was preserved for n-propanol compared to acetonitrile for the analysis of the whole protein cytochrome C and the peptide bacitracin on a column with particle and pore sizes of 5 μm and 300 Å, but slightly deteriorated for the separation of the peptides leucine–enkephaline and bacitracin on a 3 μm and 90 Å column as the peak width at half height for both peptides increased by a factor of two. The performance on the smaller dimensioned column could however be improved by running the separations at 40 °C.     

Students’ self-regulation of emotions in mathematics: an analysis of meta-emotional knowledge and skills

Over the past decade, the concept of self-regulated learning has broadened to include motivational, volitional, and emotional components next to (meta-)cognitive ones. In this article, we present a meta-emotion perspective as an essential component of a conceptual framework on self-regulation that fully acknowledges the role of emotions. Against this background, a study is presented that attempts to contribute to the clarification of the relevance and the functioning of students’ meta-emotional knowledge and emotional regulation skills in school-related mathematical activities. It investigates the coping strategies that 393 students of the second (age 14) and fourth (age 16) year of secondary school report to use to regulate their emotions in three different mathematical school settings (i.e., a mathematics test, a difficult mathematics homework, and a difficult mathematics lesson). More specifically, it aims (1) to document the nature and frequency of the reported coping strategies, and (2) to explore—for the three different mathematical school settings—relationships between these reported coping strategies and personal characteristics (i.e., students’ familiarity with the particular school settings, their track in secondary education, their achievement level, their age, and gender). The results indicate that students report to know and to make use of several coping strategies in school-related mathematical activities, and reveal that the use of these strategies is related to specific person-related characteristics. In conclusion, we elaborate on how schools and teachers can stimulate students to acquire appropriate strategies and skills to self-regulate their emotions.     

Forced vibrations of a bubble in a liquid-filled elastic vessel

There is increasing demand for accurate characterization of the in vivo behavior of microbubble agents used for ultrasound imaging and therapy. This study examines bubble-vessel interaction, in particular the propagation of disturbances along the vessel wall. Finite element simulations of a 3 μm radius microbubble suspended in a viscous liquid and enclosed in a 4 μm radius elastic vessel were performed, and the results compared with existing analytical results for wave propagation in elastic liquid-filled tubes. The vessel wall was shown to have a significant effect upon the amplitude of bubble oscillation and hence acoustic radiation from it, as well as distension of the vessel wall. It was found that the most important factor was the ratio of the excitation frequency to the natural "ring" frequency of the vessel which in turn depends upon its dimensions and mechanical properties. As this ratio increases, the motion of the vessel wall becomes increasingly localized to the site of the bubble. It was also shown that the validity of the results obtained using the applied model of vessel elasticity is limited to frequencies below the ring frequency, and this should be taken into account in the development of protocols for ultrasound safety and/or therapeutic procedures.     

A diffuse-interface method for two-phase flows with soluble surfactants

A method is presented to solve two-phase problems involving soluble surfactants. The incompressible Navier-Stokes equations are solved along with equations for the bulk and interfacial surfactant concentrations. A non-linear equation of state is used to relate the surface tension to the interfacial surfactant concentration. The method is based on the use of a diffuse interface, which allows a simple implementation using standard finite difference or finite element techniques. Here, finite difference methods on a block-structured adaptive grid are used, and the resulting equations are solved using a non-linear multigrid method. Results are presented for a drop in shear flow in both 2D and 3D, and the effect of solubility is discussed.     

Direct observation of broken time-reversal symmetry on the surface of a magnetically doped topological insulator

We study interference patterns of a magnetically doped topological insulator Bi(2-x)Fe(x)Te(3+d) by using Fourier transform scanning tunneling spectroscopy and observe several new scattering channels. A comparison with angle-resolved photoemission spectroscopy allows us to unambiguously ascertain the momentum-space origin of distinct dispersing channels along high-symmetry directions and identify those originating from time-reversal symmetry breaking. Our analysis also reveals that the surface state survives far above the energy where angle-resolved photoemission spectroscopy finds the onset of continuum bulk bands.