Back cover: Mn2+ or Mn3+? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

A new CE method with ultraviolet–visible detection was developed in this study to investigate manganese dissolution in lithium ion battery electrolytes. The aqueous running buffer based on diphosphate showed excellent stabilization of labile Mn³⁺, even under electrophoretic conditions. The method was optimized regarding the concentration of diphosphate and modifier to obtain suitable signals for quantification. Additionally, the finally obtained method was applied on carbonate-based electrolytes samples. Dissolution experiments of the cathode material LiNi_0.5Mn_1.5O₄ (lithium nickel manganese oxide [LNMO]) in aqueous diphosphate buffer at defined pH were performed to investigate the effect of a transition metal-ion-scavenger on the oxidation state of dissolved manganese. Quantification of both Mn species revealed the formation of mainly Mn³⁺, which can be attributed to a comproportionation reaction of dissolved and complexed Mn²⁺ with Mn⁴⁺ at the surface of the LNMO structure. It was also shown that the formation of Mn³⁺ increased with lower pH. In contrast, dissolution experiments of LNMO in carbonate-based electrolytes containing LIPF₆ showed only dissolution of Mn²⁺.     

Dihydrogen Adduct (Co–H2) Complexes Displaying H-Atom and Hydride Transfer

The prototypical reactivity profiles of transition metal dihydrogen complexes (M-H₂) are well-characterized with respect to oxidative addition (to afford dihydrides, M(H)₂) and as acids, heterolytically delivering H⁺ to a base and H⁻ to the metal. In the course of this study we explored plausible alternative pathways for H₂ activation, namely direct activation through H-atom or hydride transfer from the σ-H₂ adducts. To this end, we describe herein the reactivity of an isostructural pair of a neutral S= and an anionic S=0 Co-H₂ adduct, both supported by a trisphosphine borane ligand (P₃^B). The thermally stable metalloradical, (P₃^B)Co(H₂), serves as a competent precursor for hydrogen atom transfer to ^tBu₃ArO^⋅. What is more, its anionic derivative, the dihydrogen complex [(P₃^B)Co(H₂)]¹⁻, is a competent precursor for hydride transfer to BEt₃, establishing its remarkable hydricity. The latter finding is essentially without precedent among the vast number of M-H₂ complexes known.     

One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process

Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru₁/CeO₂ and Rh₁/CeO₂ SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.     

Electrospinning of a functional perfluorinated block copolymer as a powerful route for imparting superhydrophobicity and corrosion resistance to aluminum substrates

Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.     

Separation of parasites from human blood using deterministic lateral displacement

We present the use of a simple microfluidic technique to separate living parasites from human blood. Parasitic trypanosomatids cause a range of human and animal diseases. African trypanosomes, responsible for human African trypanosomiasis (sleeping sickness), live free in the blood and other tissue fluids. Diagnosis relies on detection and due to their often low numbers against an overwhelming background of predominantly red blood cells it is crucial to separate the parasites from the blood. By modifying the method of deterministic lateral displacement, confining parasites and red blood cells in channels of optimized depth which accentuates morphological differences, we were able to achieve separation thus offering a potential route to diagnostics.     

Detection of trace amounts of Ni by laser-induced fluorescence in graphite furnace with intensified charge coupled device

A laser-induced fluorescence in graphite furnace (LIF-GF) set-up has been equipped with an intensified CCD detector (ICCD) that enables simultaneous multichannel detection of large wavelength regions. The main advantages of such a system in comparison with conventional photomultiplier detection are: simultaneous detection of several fluorescence wavelengths for easy characterization of excitation and fluorescence spectra and for an increase of the absolute sensitivity and spectral selectivity; simultaneous monitoring of background signals, such as those due to matrix interferences, blackbody radiation and scattered laser light; decrease of the susceptibility to radio-frequency pick-ups emitted from the pump laser due to the delayed read-out procedure; time-resolved studies of fluorescence spectra for improved elemental selectivity or for studies of atomization processes, and a possibility to perform two-dimensional imaging of height distributions of atomization and, in combination with an imaging spectrometer, diffusion processes in the furnace. The first work on LIF-GF with ICCD detection has been performed on Ni. The most sensitive and versatile excitation and detection wavelengths have been identified. Detection limits in water solutions by the LIF-GF technique have been improved by two orders of magnitude and are found to be 0.015 pg with ICCD and 0.01 pg using a photomultiplier at the most sensitive excitation and detection wavelengths. Nickel in concentrations has been detected in aqueous standard reference samples with sodium concentrations ranging from to % (riverine water and estuarine water) with good accuracy and precision. The Ni contents of standard riverine and estuarine water were determined to 1.00 ± 0.11 and 0.75 ± 0.07 ng/ml, respectively. The certified concentrations are 1.03 ± 0.10 and 0.743 ± 0.078 .     

Identification of Compounds that Selectively Stabilize Specific G‐Quadruplex Structures by Using a Thioflavin T‐Displacement Assay as a Tool

Small molecules are used in the G‐quadruplex (G4) research field in vivo and in vitro, and there are increasing demands for ligands that selectively stabilize different G4 structures. Thioflavin T (ThT) emits an enhanced fluorescence signal when binding to G4 structures. Herein, we show that ThT can be competitively displaced by the binding of small molecules to G4 structures and develop a ThT‐displacement high‐throughput screening assay to find novel and selective G4‐binding compounds. We screened approximately 28 000 compounds by using three different G4 structures and identified eight novel G4 binders. Analysis of the structural conformation and stability of the G4 structures in presence of these compounds demonstrated that the four compounds enhance the thermal stabilization of the structures without affecting their structural conformation. In addition, all four compounds also increased the G4‐structure block of DNA synthesis by Taq DNA polymerase. Also, two of these compounds showed selectivity between certain Schizosaccharomyces pombe G4 structures, thus suggesting that these compounds or their analogues can be used as selective tools for G4 DNA studies.     

Synthesis and electron transfer studies of ruthenium-terpyridine-based dyads attached to nanostructured TiO2

A series of bis(terpyridine)RuII complexes have been prepared, where one of the terpyridines is functionalized in the 4'-position by a phosphonic or carboxylic acid group for attachment to TiO2. The other is functionalized, also in the 4'-position, by a potential electron donor. In complexes 1a, 3a, and 4a,b, this donor is tyrosine or hydrogen-bonded tyrosine, while in 2a it is carotenoic amide. The synthesis and photophysical properties of the complexes are discussed. On irradiation with visible light, the formation of a long-lived charge-separated state was anticipated, via primary electron ejection into the TiO2, followed by secondary electron transfer from the donor to the photogenerated RuIII. However, such a charge-separated state could be observed with certainty only with complex 2a. To explain the result, quantum chemical calculations were performed on the different types of complexes.