Gas-Phase Characterization of Redox-Active Manganese Complexes.

Manganese complexes exhibit a rich redox chemistry, usually accompanied by structural reorganization during the redox processes often followed by ligand dissociation or association. The push-pull ligand 2,6-diguanidylpyridine (dgpy) stabilizes manganese in the oxidation states +II, +III, and + IV in the complexes [Mn(dgpy)] ( = 2-4) without change in the coordination sphere in the condensed phase [Heinze et al., , 61, 14616].

Multi-Parameter Analysis of Nanoplastics in Flow: Taking Advantage of High Sensitivity and Time Resolution Enabled by Stimulated Raman Scattering.

Here, we demonstrate the detection of nanoplastics (NPLs) in flow with stimulated Raman scattering (SRS) for the first time. NPLs (plastic particles <1000 nm) have recently been detected in different environmental samples and personal care products. However, their characterization is still an analytical challenge.

Dynamics of carbene formation in the reaction of methane with the tantalum cation in the gas phase.

The controlled activation of methane has drawn significant attention throughout various disciplines over the last few decades. In gas-phase experiments, the use of model systems with reduced complexity compared to condensed-phase catalytic systems allows us to investigate the intrinsic reactivity of elementary reactions down to the atomic level. Methane is rather inert in chemical reactions, as the weakening or cleavage of a C-H bond is required to make use of methane as C-building block.

Ultrafast creation of a light-induced semimetallic state in strongly excited 1T-TiSe.

Screening, a ubiquitous phenomenon associated with the shielding of electric fields by surrounding charges, has been widely adopted as a means to modify a material's properties. While most studies have relied on static changes of screening through doping or gating thus far, here we demonstrate that screening can also drive the onset of distinct quantum states on the ultrafast timescale. By using time- and angle-resolved photoemission spectroscopy, we show that intense optical excitation can drive 1T-TiSe, a prototypical charge density wave material, almost instantly from a gapped into a semimetallic state.

Ta and Nb + CO: intersystem crossing in ion-molecule reactions.

The reactions of Ta and Nb with CO proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta and Nb, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta hinting at a bottleneck along the reaction path.

Cryo-IR spectroscopy and cryo-kinetics of cluster N2 adsorbate complexes of tantalum cluster cations Ta5-8.

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5-8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000 cm-1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000 cm-1, which indicate side-on μ2-κN:κN,N coordinated ones.

Cryo IR spectroscopy and cryo kinetics of dinitrogen activation and cleavage by small tantalum cluster cations.

We investigate small tantalum clusters Tan+, n = 2-4, for their capability to cleave N2 adsorption spontaneously. We utilize infrared photon dissociation (IR-PD) spectroscopy of isolated and size selected clusters under cryogenic conditions within a buffer gas filled ion trap, and we augment our experiments by quantum chemical simulations (at DFT level). All Tan+ clusters, n = 2-4, seem to cleave N2 efficiently.

Dynamics of the Oxygen Atom Transfer Reaction between Carbon Dioxide and the Tantalum Cation.

The understanding of fundamental atomic-level processes often requires well-defined model systems. The oxygen atom transfer from CO to a transition metal cation in the gas phase presents such a model system. We investigate the reaction of Ta + CO for which the formation of TaO is highly efficient and attributed to multistate reactivity.

Physicochemical characterization and quantification of nanoplastics: applicability, limitations and complementarity of batch and fractionation methods.

A comprehensive physicochemical characterization of heterogeneous nanoplastic (NPL) samples remains an analytical challenge requiring a combination of orthogonal measurement techniques to improve the accuracy and robustness of the results. Here, batch methods, including dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), tunable resistive pulse sensing (TRPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM), as well as separation/fractionation methods such as centrifugal liquid sedimentation (CLS) and field-flow fractionation (FFF)-multi-angle light scattering (MALS) combined with pyrolysis gas chromatography mass spectrometry (pyGC-MS) or Raman microspectroscopy (RM) were evaluated for NPL size, shape, and chemical composition measurements and for quantification. A set of representative/test particles of different chemical natures, including (i) polydisperse polyethylene (PE), (ii) (doped) polystyrene (PS) NPLs, (iii) titanium dioxide, and (iv) iron oxide nanoparticles (spherical and elongated), was used to assess the applicability and limitations of the selected methodologies.

In mitosis integrins reduce adhesion to extracellular matrix and strengthen adhesion to adjacent cells.

To enter mitosis, most adherent animal cells reduce adhesion, which is followed by cell rounding. How mitotic cells regulate adhesion to neighboring cells and extracellular matrix (ECM) proteins is poorly understood. Here we report that, similar to interphase, mitotic cells can employ integrins to initiate adhesion to the ECM in a kindlin- and talin-dependent manner.

Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex.

In this report, we present the dinuclear copper(II) dimethylglyoxime (H dmg) complex [Cu (H dmg)(Hdmg)(dmg)] (1), which, in contrast to its mononuclear analogue [Cu(Hdmg) ] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging μ -O-N=C-group of H dmg and thus, facilitates the nucleophilic attack of H O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH OH that, depending on the solvent, is then either oxidized or reduced.

Revealing the order parameter dynamics of 1T-TiSe[Formula: see text] following optical excitation.

The formation of a charge density wave state is characterized by an order parameter. The way it is established provides unique information on both the role that correlation plays in driving the charge density wave formation and the mechanism behind its formation. Here we use time and angle resolved photoelectron spectroscopy to optically perturb the charge-density phase in 1T-TiSe[Formula: see text] and follow the recovery of its order parameter as a function of energy, momentum and excitation density.

Quality of life in patients with Fabry's disease: a cross-sectional study of 86 adults.

Background: Fabry disease (FD) is a multi-organ disorder associated with severe physical and psychological impairments, particularly in adulthood. To date, comprehensive data on the psychological burden of FD are lacking. The present study assessed quality of life (QOL) in a representative cohort of adults with FD.

Psychosocial well-being in postpartum women with congenital heart disease.

Background: Improved treatment options for congenital heart disease (CHD) lead to a growing number of women with CHD at reproductive age. Due to physical and psychological burden, pregnancies in women with CHD often count for high-risk. Resulting emotional distress can adversely impact pregnancy, motherhood and fetal health.

Cryo infrared spectroscopy of N adsorption onto bimetallic rhodium-iron clusters in isolation.

We investigated the N adsorption behavior of bimetallic rhodium-iron cluster cations [RhFe(N)] by means of InfraRed MultiplePhotoDissociation (IR-MPD) spectroscopy in comparison with density functional theory (DFT) modeling. This approach allows us to refine our kinetic results [Ehrhard et al., J.

Kinetics of stepwise nitrogen adsorption by size-selected iron cluster cations: Evidence for size-dependent nitrogen phobia.

We present a study of stepwise cryogenic N adsorption on size-selected Fe (n = 8-20) clusters within a hexapole collision cell held at T = 21-28 K. The stoichiometries of the observed adsorption limits and the kinetic fits of stepwise N uptake reveal cluster size-dependent variations that characterize four structural regions. Exploratory density functional theory studies support tentative structural assignment in terms of icosahedral, hexagonal antiprismatic, and closely packed structural motifs.

High prevalence of falsely declaring nicotine abstinence in lung transplant candidates.

Tobacco use after lung transplantation is associated with adverse outcome. Therefore, active smoking is regarded as a contraindication for lung transplantation and should be excluded prior to placement on the waiting list. The aim of the study was to compare self-reporting with a systematic cotinine based screening approach to identify patients with active nicotine abuse.

Hydrogenation of small hydrocarbons on MgO supported Pd nanoparticles: The A-E-model expanded.

The hydrogenation of ethylene and acetylene was studied on a Pd/MgO/Mo(100) model system containing palladium particles with a narrow size distribution around Pd (Pd to Pd). Reactivity measurements were carried out in an ultrahigh vacuum chamber under isothermal conditions in the presence of deuterium. The catalyst system can readily hydrogenate both of these small molecules, and for acetylene, an alternative reaction network exists, in which it is trimerized to benzene.

Spatial distribution of zinc in the topsoil of four vegetated infiltration swales treating zinc roof runoff.

Since stormwater runoff from zinc roofs is polluted with high concentrations of zinc (Zn), runoff treatment is recommended in order to avoid harmful influences to the ecosystem. For the retention of Zn, vegetated infiltration swales with a topsoil layer are often used as decentralized Sustainable Urban Drainage Systems (SUDS). The aim of this study was to assess the risks of groundwater contamination due to infiltration of stormwater runoff of a Zn roof using infiltration swales.

Heavy metal removal mechanisms of sorptive filter materials for road runoff treatment and remobilization under de-icing salt applications.

The objective of this research study was to elucidate the removal and remobilization behaviors of five heavy metals (i.e., Cd, Cu, Ni, Pb, and Zn) that had been fixed onto sorptive filter materials used in decentralized stormwater treatment systems receiving traffic area runoff.

A novel test method to determine the filter material service life of decentralized systems treating runoff from traffic areas.

In recent years, there has been a significant increase in the development and application of technical decentralized filter systems for the treatment of runoff from traffic areas. However, there are still many uncertainties regarding the service life and the performance of filter materials that are employed in decentralized treatment systems. These filter media are designed to prevent the transport of pollutants into the environment.

Evaluation of site-specific factors influencing heavy metal contents in the topsoil of vegetated infiltration swales.

Stormwater runoff of traffic areas is usually polluted by organic and inorganic substances and must be treated prior to discharge into groundwater. One widely used treatment method is infiltrating the runoff over the topsoil of vegetated swales. The aim of this study was to evaluate the factors influencing the heavy metal contents in such topsoil layers of vegetated infiltration swales near highways, roads, and parking lots.

Critical review of heavy metal pollution of traffic area runoff: Occurrence, influencing factors, and partitioning.

A dataset of 294 monitored sites from six continents (Africa, Asia, Australia, Europe, North and South America) was compiled and evaluated to characterize the occurrence and fate of heavy metals in eight traffic area categories (parking lots, bridges, and three types each of both roads and highways). In addition, site-specific (fixed and climatic) and method-specific (related to sample collection, preparation, and analysis) factors that influence the results of the studies are summarized. These factors should be considered in site descriptions, conducting monitoring programs, and implementing a database for further research.