2]borametallocenophanes of group 4 metals: synthesis and structure

We report a series of [2]borametallocenophanes of Ti, Zr, and Hf with various ligand systems. The ligands have been synthesized in high yields starting from 1,2-dibromo-1,2-bis(dimethylamino)diborane(4) upon reaction with Na[C5H5] and Li[C13H9], respectively. All compounds were fully characterized by multinuclear NMR spectroscopy and, for selected examples, by X-ray analysis.     

Structural modifications of serum transthyretin in rats during protein-energy malnutrition

Transthyretin (TTR) is a sensitive marker of protein-energy malnutrition and changes in serum and expression levels during protein and energy deficiency are well described. However, little is known about structural modifications of TTR during protein and/or energy deprivation. Therefore, the aim of this study was to determine the effects of protein inadequacies on post-translational modifications of TTR. For this purpose, male Wistar rats were fed a diet with either casein or gelatine as sole protein source subsequent to a protein wash-out period. Changes in TTR serum levels as well as other markers of nutritional status as body weight, food consumption, total serum protein and serum RBP4 levels as well as antioxidative capacity were determined. Post-translational modifications of TTR were examined by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) analysis. The rats from the gelatine group revealed a marked change in the post-translational modification pattern of TTR which was reflected by a significant elevation of sulfonated TTR and which was inversely correlated to the antioxidative capacity. Additionally, the elevation of sulfonated TTR was accompanied by a decrease in body weight and food consumption, low antioxidative capacity as well as a deprivation of serum TTR, RBP4 and total serum protein levels in the animals of the gelatine group. Protein-energy malnutrition leads therefore next to changes in TTR serum concentration, also to changes in the post-translational modification pattern of TTR. Such changes are probably induced by protein-energy malnutrition-driven oxidative stress and might be linked to alterations in protein function and stability.     

Front Cover: Method development for the investigation of Mn2+/3+, Cu2+, Co2+, and Ni2+ with capillary electrophoresis hyphenated to inductively coupled plasma–mass spectrometry

The lifetime of lithium ion batteries (LIBs) decreases under continuous cycling due to various degradation processes, such as dissolution of transition metals (TMs) from the electrodes. Therefore, suitable methods to analyze the oxidation states of TMs are mandatory to better understand the dissolution mechanisms of TMs from positive and negative electrodes (LIBs). To investigate the dissolution of Mn²⁺ and Mn³⁺ in electrolytes of LIBs, a previously implemented capillary electrophoresis (CE) method with UV/Vis spectroscopy detection was further developed with the aim of higher sensitivities and additional detection of other dissolved divalent TMs such as Co²⁺, Ni²⁺, and Cu²⁺. Therefore, inductively coupled plasma–mass spectrometry was applied instead of UV/Vis for detection. This also allows the use of Ga³⁺ instead of the previously used Cu²⁺ as an internal standard, which solves the limitation of this method for cycled LIBs due to copper dissolution from the copper-based current collector. The CE buffer based on sodium diphosphate as complexing agent for the stabilization of Mn³⁺ and cetyltrimethylammonium bromide as dynamic capillary wall modifier was optimized in terms of concentrations and pH. Finally, both manganese species and Co²⁺, Ni²⁺, and Cu²⁺ could be analyzed within 15 min. With this improved method, the dissolution of TMs in LIBs for positive electrode materials such as LiNi_0.5Mn_1.5O₄ (LNMO) or LiNi_xCo_yMn_zO₂ (NCM, x + y + z = 1) can be studied in future in more detail.     

Activating a Low Overpotential CO2 Reduction Mechanism by a Strategic Ligand Modification on a Ruthenium Polypyridyl Catalyst

The introduction of a simple methyl substituent on the bipyridine ligand of [Ru(tBu₃tpy)(bpy)(NCCH₃)]²⁺ (tBu₃tpy=4,4′,4′′‐tri‐tert‐butyl‐2,2′:6′,2′′‐terpyridine; bpy=2,2′‐bipyridine) gives rise to a highly active electrocatalyst for the reduction of CO₂ to CO. The methyl group enables CO₂ binding already at the one‐electron reduced state of the complex to enter a previously not accessible catalytic cycle that operates at the potential of the first reduction. The complex turns over with a Faradaic efficiency close to unity and at an overpotential that is amongst the lowest ever reported for homogenous CO₂ reduction catalysts.     

Facilitated hydride binding in an Fe-Fe hydrogenase active-site biomimic revealed by X-ray absorption spectroscopy and DFT calculations

Iron-only hydrogenases are high-efficiency biocatalysts for the synthesis and cleavage of molecular hydrogen. Their active site is a diiron center, which carries CO and CN ligands. Remarkably, the two iron atoms likely are connected by a non-protein azadithiolate (adt = S-CH2-NH-CH2-S). To dwell on the role of the adt in H2 catalysis, a specific biomimetic diiron compound, 1 = [Fe2(mu-adt-CH2-Ph)(CO)4(PMe3)2], with unprecedented positive reduction potential, has been synthesized and crystallized previously. It comprises two protonation sites, the N-benzyl-adt nitrogen that can hold a proton (H) and the Fe-Fe bond that will formally carry a hydride (Hy). We investigated changes in the solution structure of 1 in its four different protonation states (1', [1H]+, [1HHy]2+, and [1Hy]+) by X-ray absorption spectroscopy at the iron K-edge. EXAFS reveals that already protonation at the adt nitrogen atom causes a change of the ligand geometry involving a significant lengthening of the Fe-Fe distance and CO and PMe3 repositioning, respectively, thereby facilitating the subsequent binding of a bridging hydride. Hydride binding clearly is discernible in the XANES spectra of [1HHy]2+ and [1Hy]+. DFT calculations are in excellent agreement with the experimentally derived structural parameters and provide complementary insights into the electronic structure of the four protonation states. In the iron-only hydrogenases, protonation of the putative adt ligand may cause the bridging CO to move to a terminal position, thereby preparing the active site for hydride binding en route to H2 formation.     

Multidimensional electrochemical imaging in materials science

In the past 20 years the characterization of electroactive surfaces and electrode reactions by scanning probe techniques has advanced significantly, benefiting from instrumental and methodological developments in the field. Electrochemical and electrical analysis instruments are attractive tools for identifying regions of different electrochemical properties and chemical reactivity and contribute to the advancement of molecular electronics. Besides their function as a surface analytical device, they have proved to be unique tools for local synthesis of polymers, metal depots, clusters, etc. This review will focus primarily on progress made by use of scanning electrochemical microscopy (SECM), conductive AFM (C-AFM), electrochemical scanning tunneling microscopy (EC-STM), and surface potential measurements, for example Kelvin probe force microscopy (KFM), for multidimensional imaging of potential-dependent processes on metals and electrified surfaces modified with polymers and self assembled monolayers. Figure Electrochemical and electrical tools like scanning electrochemical microscopy, conductive atomic force microscopy, electrochemical scannig tunneling microscopy and Kelvin probe force microscopy (see figure) are powerful tools for the multidimensional imaging of potential-dependent processes on metals and electrified surfaces modified with polymers and self assembled monolayers.