Synthesis and Characterization of Bis(pyridylimino)isoindolide Alkali Metal Complexes in Three Redox States

Non-innocent ligands (NILs) like bis(pyridylimino)isoindolide (BPI) play crucial roles in coordination chemistry, biosciences, catalysis and material sciences. Investigating the isolated redox states of NILs is inevitable for understanding their redox-activity and fine-tuning the properties of corresponding metal complexes. The limited number of fundamental studies on the coordination behavior and redox chemistry of reduced BPI species is suggested to hamper further applications of the title compounds. This work describes for the first time the isolation of alkali metal complexes of BPI and Me2BPI in three different oxidation states and their characterization by means of NMR or EPR spectroscopy, DFT calculations, and SC-XRD studies. The latter revealed the connection between bond orders in the ligand scaffold and its oxidation state. The paramagnetic compound Me2BPI-K2 was isolated as a coordination copolymer with 18-crown-6, which enabled the characterization of the dianionic BPI radical. Furthermore, the so-far unknown trianionic state of BPI was reported by the isolation of BPI-K3. This divulges an unprecedented bis(amidinato)isoindolide coordination mode

Trace metal accumulation in hair and skin of the harbour seal, Phoca vitulina

Skin and hair samples of harbour seals (Phoca vitulina) found dead along the west coast of northern Germany in 1988 were analysed for total mercury, cadmium and lead. Cadmium and lead concentrations were below the detection limit in most skin samples. The mercury content of the hair (median: 23.1 μg g−1 wet wt) was several magnitudes higher than the mercury content of the skin (0.27 μg g−1 wet wt). Mercury concentrations in hair samples were significantly higher than lead concentrations (0.54 μg g−1 wet wt), which significantly exceeded cadmium levels (0.09 μg g−1 wet wt). Female seals revealed lower cadmium concentrations in the hair than male seals. Accumulations of metals with age were observed for cadmium and lead in hair samples and for mercury in skin samples of male seals. A connection between metal accumulation and pigmentation or rather moult was clearly recognizable

Chronic anti-Thy-1 nephritis is aggravated in the nonclipped but not in the clipped kidney of Goldblatt hypertensive rats

Chronic anti-Thy-1 nephritis is aggravated in the nonclipped but not in the clipped kidney of Goldblatt hypertensive rats.BackgroundWe have previously shown that renovascular hypertension does not inhibit healing of the acute Thy-1 nephritis. To test whether a chronic model of the Thy-1 nephritis is more susceptible to high blood pressure, the repetitive hit model was evaluated in rats with 2-kidney, 1-clip Goldblatt hypertension.MethodsSix weeks after initiation of 2-kidney, 1-clip hypertension, chronic Thy-1 glomerulonephritis was induced in hypertensive rats by four consecutive injections of rabbit antiserum in weekly intervals. Renal structure and function were examined two weeks after the last injection. Glomerular binding of rabbit IgG as well as expression of transforming growth factor-beta (TGF-β), α-smooth muscle actin (α-SMA) and cyclooxygenase (COX)-1 and -2 were evaluated by Western blotting.ResultsSimilar glomerular deposition of rabbit IgG was detected in normotensive rats and in both kidneys of Goldblatt hypertensive rats indicating similar delivery and binding of the heterologous antibody. Induction of the repetitive Thy-1 model significantly enhanced glomerular damage in the nonclipped kidney and increased albuminuria. Surprisingly, no glomerular damage developed in the clipped kidney of nephritic hypertensive rats. In contrast, increased glomerular volume and increased expression of TGF-β, α-SMA as well as COX-1 and COX-2 were found in normotensive nephritic rats and in both kidneys of nephritic hypertensive rats.ConclusionGlomerular and tubulointerstitial damage of the chronic Thy-1 model is dramatically enhanced in the nonclipped kidneys of Goldblatt hypertensive rats. In contrast, the clipped kidney is completely protected from this immunological injury despite similar activation of glomerular cells, induction of TGF-β, COX-1 and COX-2 and glomerular hypertrophy

High-brightness broad-area diode lasers with enhanced self-aligned lateral structure

Broad-area diode lasers with increased brightness and efficiency are presented, which are fabricated using an enhanced self-aligned lateral structure by means of a two-step epitaxial growth process with an intermediate etching step. In this structure, current-blocking layers in the device edges ensure current confinement under the central stripe, which can limit the detrimental effects of current spreading and lateral carrier accumulation on beam quality. It also minimizes losses at stripe edges, thus lowering the lasing threshold and increasing conversion efficiency, while maintaining high polarization purity. In the first realization of this structure, the current block is integrated within an extreme-triple-asymmetric epitaxial design with a thin p-doped side, meaning that the distance between the current block and the active zone can be minimized without added process complexity. Using this configuration, enhanced self-aligned structure devices with 90 µm stripe width and 4 mm resonator length show up to 20% lower threshold current, 21% narrower beam waist, and slightly higher (1.03 ) peak efficiency in comparison to reference devices with the same dimensions, while slope, divergence angle and polarization purity remain almost unchanged. These results correspond to an increase in brightness by up to 25%, and measurement results of devices with varying stripe widths follow the same trend. © 2020 The Author(s). Published by IOP Publishing Ltd

Methods for removal of unwanted signals from gravity time-series : comparison using linear techniques complemented with analysis of system dynamics

We thanks the participants of the 35th General Assembly of the European Seismological Commission for comments on preliminary results. The authors are grateful to all IGETS contributors, particularly to the station operators and to ISDC/GFZ-Potsdam for providing the original gravity data used in this study. We also thank the developers of ATLANTIDA3.1 and UTide. Part of this work was performed using the ICSMB High Performance Computing Cluster, University of Aberdeen. We also thanks M. Thiel and A. Moura for reviewing a preliminary version and making comments on the methods section and M.A. Ara´ujo for comments on Lyapunov exponents. Funding: A. Valencio is supported by CNPq, Brazil [206246/2014-5]; and received a travel grant from the School of Natural and Computing Sciences, University of Aberdeen [PO2073498], for a presentation including preliminary results.Peer reviewedPostprintPublisher PD

Bifunctional chalcogen linkers for the stepwise generation of multimetallic assemblies and functionalized nanoparticles

The disulfide ligand (SC6H4CO2H-4)2 acts as a simple but versatile linker for a range of group 8 transition metals through reaction of the oxygen donors. This leads to a range of homobimetallic ruthenium and osmium alkenyl compounds, [{M(CH═CHR)(CO)(PPh3)2(O2CC6H4S-4)}2] (M = Ru, Os; R = C6H4Me-4). Additional metal-based functionality can be added through the use of precursors incorporating rhenium bipyridine units (R = (bpy)ReCl(CO)3). The more robust diphosphine ligands in [{Ru(dppm)2(O2CC6H4S-4)}2](2+) (dppm = diphenylphosphinomethane) allow reduction of the disulfide bond with sodium borohydride to yield the thiol complex [Ru(O2CC6H4SH-4)(dppm)2](+). This complex reacts with [AuCl(PPh3)] to afford the bimetallic compound [Ru(dppm)2(O2CC6H4S-4)Au(PPh3)](+). However, an improved route to the same and related heterobimetallic compounds is provided by the reaction of cis-[RuCl2(dppm)2] with [Au(SC6H4CO2H-4)(L)] (L = PPh3, PCy3, PMe3, IDip) in the presence of base and NH4PF6 (IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The heterotrimetallic compound [Au(SC6H4CO2Ru(dppm)2)2](+) is accessible through the reaction of the homoleptic gold(I) dithiolate [Au(SC6H4CO2H-4)2]PPN (PPN = bis(triphenylphosphine)iminium) with cis-[RuCl2(dppm)2]. Without departure from the same methodology, greater complexity can be incorporated into the system to provide the penta- and heptametallic assemblies [(dppf){AuSC6H4CO2Ru(dppm)2}2](2+) and [(dppf){AuSC6H4CO2Os(CH═CH-bpyReCl(CO)3)(CO)(PPh3)2}2]. The same stepwise approach provides the dinuclear organometallic complexes [(L)Au(SC6H4CO2-4)M(CH═CHC6H4Me-4)(CO)(PPh3)2] (M = Ru, Os; L = PPh3, IDip). Complexes containing three metals from different groups of the periodic table [(L)Au(SC6H4CO2-4)M{CH═CH-bpyReCl(CO)3}(CO)(PPh3)2] (M = Ru, Os) can also be prepared, with one ruthenium example (L = PPh3) being structurally characterized. In order to illustrate the versatility of this approach, the synthesis and characterization (IR and NMR spectroscopy, TEM, EDS, and TGA) of the functionalized gold and palladium nanoparticles Au@[SC6H4CO2Ru(dppm)2](+) and Pd@[SC6H4CO2Ru(dppm)2](+) is reported