On-line electrochemically controlled solid-phase extraction interfaced to electrospray and inductively coupled plasma mass spectrometry

Electrochemically controlled solid-phase extractions of anions were interfaced on-line to electrospray mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), using polypyrrole coated electrodes and a thin-layer electrochemical (EC) flow cell. The results indicate that electrochemically controlled solid-phase extraction (EC-SPE) can be used as a versatile potential controlled sample preparation technique for a range of anions and that the properties of the polypyrrole coatings can be modified by altering the electrodeposition conditions. In the present study, the influence of interfering anions (i.e., fluoride and sulfate), and the anion used during the electropolymerisation, on the bromide extraction recovery was investigated for EC-SPE interfaced to ICP-MS. The results of these experiments show that the interference due to the presence of similar concentrations of sulfate can be reduced when using a polypyrrole coating electropolymerised in the presence of bromide ions. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements were also used to study the morphology of the coatings, as well as the variations in the film thickness within the coatings. The effect of different desorption techniques on the bromide preconcentration factor in the ICP-MS on-line flow system was also examined. Stopped-flow desorption was found to give rise to significantly increased preconcentration factors in comparison with desorptions in flowing solutions. While the desorption efficiency depends on the type of desorption electrolyte (the electrolyte in which the desorption takes place), due to the competing influx of cations, the influence of the pH on the switching charge of the polypyrrole coating was found to be small, at constant ionic strength. To study the applicability of the EC-SPE technique with respect to real samples, investigations were also made with tap water samples spiked with different bromide concentrations. The results of these experiments, which were carried out using a modified thin-layer EC flow cell allowing in situ polymerisation of polypyrrole yielding a polymer plug covering the cross section of the channel, demonstrate that 3 microM concentrations of bromide could be detected in the tap water sample. This demonstrates that the extraction technique allows extractions of low concentrations of ions in the presence of significantly higher concentrations of other similar ions. The fact that the extraction and desorption steps are electrochemically controlled makes EC-SPE particularly well suited for inclusion in miniaturised lab-on-a-chip systems.     

Discovery of Highly Selective Alkyne Semihydrogenation Catalysts Based on First‐Row Transition‐Metallated Porous Organic Polymers

Five different first‐row transition metal precursors (V^III, Cr^III, Mn^II, Co^II, Ni^II) were successfully incorporated into a catechol porous organic polymer (POP) and characterized using ATR‐IR and XAS analysis. The resulting metallated POPs were then evaluated for catalytic alkyne hydrogenation using high‐throughput screening techniques. All POPs were unexpectedly found to be active and selective catalysts for alkyne semihydrogenation. Three of the metallated POPs (V, Cr, Mn) are the first of their kind to be active single‐site hydrogenation catalysts. These results highlight the advantages of using a POP platform to develop new catalysts which are otherwise difficult to achieve through traditional heterogeneous and homogeneous routes.     

Further on creating normal density functions in Microsoft<Superscript>®</Superscript> Excel

Simulations play an increasing role in metrology and analytical chemistry, particularly the use of simulated normal distributions. Microsoft Excel is available to almost everybody and normal distributions can be simulated using either an innate function or other algorithms. We explore the success of five different algorithms to simulate normal distributions and compare the outcome with a simulation coded in R. The normality of 10⁶ data points simulated by the chosen algorithms was tested by different recognized statistical procedures and Q–Q plots. They all failed the statistical procedures, but evaluating the Q–Q plots revealed different types of deviations. It also showed that the deviations, although statistically significant, most likely do not have any practical relevance in laboratory work.     

Front Cover: Twisting versus Delocalization in CAAC- and NHC-Stabilized Boron-Based Biradicals: The Roles of Sterics and Electronics (Chem. Eur. J. 16/2021)

Invited for the cover of this issue is Bernd Engels, Holger Braunschweig, Volker Engel and their coworkers at University of Würzburg. The image depicts bridged boron compounds which possess fascinating relationships between their composition and their geometrical and electronic structures, the latter ranging from closed-shell to biradical triplet or singlet ground state. Read the full text of the article at 10.1002/chem.202004619 .     

Efficiency of high‐performance discontinuous Galerkin spectral element methods for under‐resolved turbulent incompressible flows

The present paper addresses the numerical solution of turbulent flows with high‐order discontinuous Galerkin methods for discretizing the incompressible Navier‐Stokes equations. The efficiency of high‐order methods when applied to under‐resolved problems is an open issue in the literature. This topic is carefully investigated in the present work by the example of the three‐dimensional Taylor‐Green vortex problem. Our implementation is based on a generic high‐performance framework for matrix‐free evaluation of finite element operators with one of the best realizations currently known. We present a methodology to systematically analyze the efficiency of the incompressible Navier‐Stokes solver for high polynomial degrees. Due to the absence of optimal rates of convergence in the under‐resolved regime, our results reveal that demonstrating improved efficiency of high‐order methods is a challenging task and that optimal computational complexity of solvers and preconditioners as well as matrix‐free implementations are necessary ingredients in achieving the goal of better solution quality at the same computational costs already for a geometrically simple problem such as the Taylor‐Green vortex. Although the analysis is performed for a Cartesian geometry, our approach is generic and can be applied to arbitrary geometries. We present excellent performance numbers on modern cache‐based computer architectures achieving a throughput for operator evaluation of 3·10⁸ up to 1·10⁹ DoFs/s (degrees of freedom per second) on one Intel Haswell node with 28 cores. Compared to performance results published within the last five years for high‐order discontinuous Galerkin discretizations of the compressible Navier‐Stokes equations, our approach reduces computational costs by more than one order of magnitude for the same setup.     

Chapter model systems in heterogeneous catalysis at the atomic level: a personal view

The review presents an overview of studies in the surface science of oxide and related surfaces with an emphasis of the studies performed in the authors' group. Novel instruments and technique developments, as well as their applications are reported, in an attempt to cover studies on model systems of increasing complexity, including some of the key ingredients of an industrially applied heterogeneous catalyst and its fabrication. The review is intended to demonstrate the power of model studies in understanding heterogeneous catalysis at the atomic level. The studies include those on supported nano-particles, both, prepared in vacuum and from solution, interaction of surfaces and the underlying bulk with molecules from the gas phase, strong metal support interaction, as well as the first attempt to include studies on reactions in confined spaces.