Isolation, Characterization and Reactivity of Key Intermediates Relevant to Reductive (Electro)catalysis with Cp*Rh Complexes Containing Pyridyl-MIC (MIC=Mesoionic Carbene) Ligands

In recent years, metal complexes of pyridyl-mesoionic carbene (MIC) ligands have been reported as excellent homogeneous and molecular electrocatalysts. In combination with group 9 metals, such ligands form highly active catalysts for hydrogenation/transfer hydrogenation/hydrosilylation catalysis and electrocatalysts for dihydrogen production. Despite such progress, very little is known about the structural/electrochemical/spectroscopic properties of crucial intermediates for such catalytic reactions with these ligands: solvato complexes, reduced complexes and hydridic species. We present here a comprehensive study involving the isolation, crystallographic characterization, electrochemical/spectroelectrochemical/theoretical investigations, and in-situ reactivity studies of all the aforementioned crucial intermediates involving Cp*Rh and pyridyl-MIC ligands. A detailed mechanistic study of the precatalytic activation of [RhCp*] complexes with pyridyl-MIC ligands is presented. Intriguingly, amphiphilicity of the [RhCp*]-hydride complexes was observed, displaying the substrate dependent transfer of H+, H or H−. To the best of our knowledge, this study is the first of its kind targeting intermediates and reactive species involving metal complexes of pyridyl-MIC ligands and investigating the interconversion amongst them

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2′-bipyridine) of the archetypical [Ru(bpy)3]2+ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)3]2+ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs

Mechanisms and pathways of Toxoplasma gondii transepithelial migration

Toxoplasma gondii is a ubiquitous parasite and a prevalent food-borne parasitic pathogen. Infection of the host occurs principally through oral consumption of contaminated food and water with the gastrointestinal tract being the primary route for entry into the host. To promote infection, T. gondii has evolved highly specialized strategies for rapid traversal of the single cell thick intestinal epithelial barrier. Parasite transmigration via the paracellular pathway between adjacent cells enables parasite dissemination to secondary sites of infection where chronic infection of muscle and brain tissue is established. It has recently been proposed that parasite interactions with the integral tight junction (TJ) protein occludin influences parasite transmigration of the intestinal epithelium. We review here the emerging mechanisms of T. gondii transmigration of the small intestinal epithelium alongside the developing role played in modulating the wider TJ-associated proteome to rewire host cell regulatory systems for the benefit of the parasite

Dew formation on the surface of biological soil crusts in central European sand ecosystems

Dew formation was investigated in three developmental stages of biological soil crusts (BSC), which were collected along a catena of an inland dune and in the initial substrate. The Penman equation, which was developed for saturated surfaces, was modified for unsaturated surfaces and used for prediction of dewfall rates. The levels of surface saturation required for this approach were predicted using the water retention functions and the thicknesses of the BSCs. During a first field campaign (2–3 August 2011), dewfall increased from 0.042 kg m<sup>−2</sup> for the initial sandy substrate to 0.058, 0.143 and 0.178 kg m<sup>−2</sup> for crusts 1 to 3, respectively. During a second field campaign (17–18 August 2011), where dew formation was recorded in 1.5 to 2.75-h intervals after installation at 21:30 CEST, dewfall increased from 0.011 kg m<sup>−2</sup> for the initial sandy substrate to 0.013, 0.028 and 0.055 kg m<sup>−2</sup> for crusts 1 to 3, respectively. Dewfall rates remained on low levels for the substrate and for crust 1, and decreased overnight for crusts 2 and 3 (with crust 3 > crust 2 > crust 1 throughout the campaign). Dew formation was well reflected by the model response. The suggested mechanism of dew formation involves a delay in water saturation in near-surface soil pores and extracellular polymeric substances (EPS) where the crusts were thicker and where the water capacity was high, resulting in elevated vapor flux towards the surface. The results also indicate that the amount of dewfall was too low to saturate the BSCs and to observe water flow into deeper soil. Analysis of the soil water retention curves revealed that, despite the sandy mineral matrix, moist crusts clogged by swollen EPS pores exhibited a clay-like behavior. It is hypothesized that BSCs gain double benefit from suppressing their competitors by runoff generation and from improving their water supply by dew collection. Despite higher amounts of dew, the water availability to the crust community decreases with crust development, which may be compensated by ecophysiological adaptation of crust organisms, and which may further suppress higher vegetation or mosses

What is the potential benefit of pre-hospital extracorporeal cardiopulmonary resuscitation for patients with an out-of-hospital cardiac arrest?:A predictive modelling study

AIM: In this predictive modelling study we aimed to investigate how many patients with an out-of-hospital cardiac arrest (OHCA) would benefit from pre-hospital as opposed to in-hospital initiation of extracorporeal cardiopulmonary resuscitation (ECPR).METHODS: A temporal spatial analysis of Utstein data was performed for all adult patients with a non-traumatic OHCA attended by three emergency medical services (EMS) covering the north of the Netherlands during a one-year period. Patients were considered potentially eligible for ECPR if they had a witnessed arrest with immediate bystander CPR, an initial shockable rhythm (or signs of life during resuscitation) and could be presented in an ECPR-centre within 45 minutes of the arrest. Endpoint of interest was defined as the hypothetical number of ECPR eligible patients after 10, 15 and 20 minutes of conventional CPR and upon (hypothetical) arrival in an ECPR-centre as a fraction of the total number of OHCA patients attended by EMS.RESULTS: During the study period 622 OHCA patients were attended, of which 200 (32%) met ECPR eligibility criteria upon EMS arrival. The optimal transition point between conventional CPR and ECPR was found to be after 15 minutes. Hypothetical intra-arrest transport of all patients in whom no return of spontaneous circulation (ROSC) was obtained after that point (n = 84) would have yielded 16/622 (2.5%) patients being potentially ECPR eligible upon hospital arrival (average low-flow time 52 minutes), whereas on-scene initiation of ECPR would have resulted in 84/622 (13.5%) potential candidates (average estimated low-flow time 24 minutes before cannulation).CONCLUSION: Even in healthcare systems with relatively short transport distances to hospital, consideration should be given to pre-hospital initiation of ECPR for OHCA as it shortens low-flow time and increases the number of potentially eligible patients.</p

Atomic layer deposition of NiO applied in a monolithic perovskite/PERC tandem cell

Monolithic perovskite/silicon tandem photovoltaics have fueled major research efforts as well as gaining rapid industrial interest. So far, most of the literature has focused on the use of currently more expensive silicon heterojunction bottom cell technology. This work demonstrates a perovskite/silicon tandem solar cell based on the industrially dominant passivated emitter and rear cell (PERC) technology. In detail, we investigate a tunnel recombination junction (TRJ) consisting of ITO/NiO/2-(9H-carbazol-9-yl)ethyl] phosphonic acid (2PACz) and compare it with an ITO/2PACz TRJ. Specifically, the NiO layer is deposited by atomic layer deposition (ALD). Although ITO/2PACz-based tandem devices can reach more than 24% conversion efficiency, we observe that they suffer from a large spread in photovoltaic parameters due to electrical shunts in the perovskite top cell, caused by the inhomogeneity of the 2PACz layer on ITO. Instead, when ALD NiO is sandwiched between 2PACz and ITO, the surface coverage of 2PACz improves and the yield of the devices, in terms of all device parameters, also improves, i.e., the standard deviation decreases from 4.6% with ITO/2PACz to 2.0% with ITO/NiO/2PACz. In conclusion, thanks to the presence of NiO, the TRJ consisting of ITO/NiO/2PACz leads to a 23.7% efficient tandem device with narrow device efficiency distribution

Factors That Complicated the Implementation of a Program of Donation After Unexpected Circulatory Death of Lungs and Kidneys. Lessons Learned From a Regional Trial in the Netherlands

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Rainfall forecasting using PSPline and rice production with ocean-atmosphere interaction

The role of climate can be affected by plants. The weather can accelerate and multiply the existence of various plant pests and diseases, accelerate the growth and development of grass among plants, and encourage the emergence of infection and significant damage to plants. The elements of climate that affect the growth of plants are one of them is rainfall. In this paper, we performed the simulation using the non-parametric penalized spline (PSPLINE) method and studied the effect on rice production in Lampung. It can be concluded that the increasing fluctuation, frequency, and intensity of climate anomalies in the last decade caused by the ENSO phenomenon have an impact on changes in distribution patterns, intensity, and period of the wet season so that the start of the rainy season and the dry season becomes too late. As a result, there is a seasonal shift from normal average conditions that can ultimately have severe implications for food crops. In a nutshell penalized spline gives high accuracy wit

PIP5KIβ Selectively Modulates Apical Endocytosis in Polarized Renal Epithelial Cells

Localized synthesis of phosphatidylinositol 4,5-bisphosphate [PtdIns(4,5)P2] at clathrin coated pits (CCPs) is crucial for the recruitment of adaptors and other components of the internalization machinery, as well as for regulating actin dynamics during endocytosis. PtdIns(4,5)P2 is synthesized from phosphatidylinositol 4-phosphate by any of three phosphatidylinositol 5-kinase type I (PIP5KI) isoforms (α, β or γ). PIP5KIβ localizes almost exclusively to the apical surface in polarized mouse cortical collecting duct cells, whereas the other isoforms have a less polarized membrane distribution. We therefore investigated the role of PIP5KI isoforms in endocytosis at the apical and basolateral domains. Endocytosis at the apical surface is known to occur more slowly than at the basolateral surface. Apical endocytosis was selectively stimulated by overexpression of PIP5KIβ whereas the other isoforms had no effect on either apical or basolateral internalization. We found no difference in the affinity for PtdIns(4,5)P2-containing liposomes of the PtdIns(4,5)P2 binding domains of epsin and Dab2, consistent with a generic effect of elevated PtdIns(4,5)P2 on apical endocytosis. Additionally, using apical total internal reflection fluorescence imaging and electron microscopy we found that cells overexpressing PIP5KIβ have fewer apical CCPs but more internalized coated structures than control cells, consistent with enhanced maturation of apical CCPs. Together, our results suggest that synthesis of PtdIns(4,5)P2 mediated by PIP5KIβ is rate limiting for apical but not basolateral endocytosis in polarized kidney cells. PtdIns(4,5)P2 may be required to overcome specific structural constraints that limit the efficiency of apical endocytosis. © 2013 Szalinski et al