Hobauer6874
We report a strategy for effecting catalytic, enantioselective carbocationic rearrangements through the intermediacy of alkyl iodanes as stereodefined carbocation equivalents. Asymmetric Wagner-Meerwein rearrangements of β-substituted styrenes are catalyzed by the C2-symmetric aryl iodide 1 to provide access to enantioenriched 1,3-difluorinated molecules possessing interesting and well-defined conformational properties. Hammett and kinetic isotope effect studies, in combination with computational investigations, reveal that two different mechanisms are operative in these rearrangement reactions, with the pathway depending on the identity of the migrating group. In reactions involving alkyl-group migration, intermolecular fluoride attack is product- and enantio-determining. In contrast, reactions in which aryl rearrangement occurs proceed through an enantiodetermining intramolecular 1,2-migration prior to fluorination. The fact that both pathways are promoted by the same chiral aryl iodide catalyst with high enantioselectivity provides a compelling illustration of generality across reaction mechanisms in asymmetric catalysis.The outbreak of SARS-CoV-2 has made us all think critically about hospital indoor air quality and the approaches to remove, dilute, and disinfect pathogenic organisms from the hospital environment. While specific aspects of the coronavirus infectivity, spread, and routes of transmission are still under rigorous investigation, it seems that a recollection of knowledge from the literature can provide useful lessons to cope with this new situation. https://www.selleckchem.com/products/nu7441.html As a result, a systematic literature review was conducted on the safety of air filtration and air recirculation in healthcare premises. This review targeted a wide range of evidence from codes and regulations, to peer-reviewed publications, and best practice standards. The literature search resulted in 394 publications, of which 109 documents were included in the final review. Overall, even though solid evidence to support current practice is very scarce, proper filtration remains one important approach to maintain the cleanliness of indoor air in hospitals. Given the rather large physical footprint of the filtration system, a range of short-term and long-term solutions from the literature are collected. Nonetheless, there is a need for a rigorous and feasible line of research in the area of air filtration and recirculation in healthcare facilities. Such efforts can enhance the performance of healthcare facilities under normal conditions or during a pandemic. Past innovations can be adopted for the new outbreak at low-to-minimal cost.The dominant intensity of parity-forbidden intra-4f transitions of europium(III) over O → Eu charge-transfer band (CTB) intensity is against common perceptions, yet this trend is observed in many germanate hosts and has not been rationalized so far. In search of a plausible explanation for this unusual trend, present work reports an experimental and theoretical investigations in conjunction on two sibling germanate host, namely, Y2GeO5 and Y2Ge2O7 having dopant Eu3+ in their respective YO7 polyhedra. Whereas for Y2GeO5Eu3+, the CTB is more intense than the intra-4f transitions in the excitation spectrum, in the case of Y2Ge2O7Eu3+, the relative intensities of CTB and intra-4f transitions are reversed. Comparative structural analysis reveals that Eu3+ present in YO7 of Y2GeO5 has a greater number of tetra-coordinated oxygen (Otetra) and yttrium atom as first and second neighbors, respectively (Eu3+-Otetra-Y3+ linkages). Conversely, in Y2Ge2O7 host, the Eu3+ ion mostly has tricoordinated oxygen (Otri) as its neted to other inorganic oxides having EuO x polyhedra surrounded by covalent units like PO4, SiO4, etc. and have a prevailing number of low-coordinated oxygen atoms and highly charged small cation in the first and second coordination shells, respectively. The optical basicity concept is also found to endorse our explanation. These remarkable generic inferences will pave the rational way for designing efficient phosphors for solid-state lighting.Orange, transparent crystals of [BMIm]2[Mn(CO)3(GeI3)3] (BMIm 1-butyl-3-methylimidazolium) are obtained by reacting GeI4, [Mn(CO)6][AlCl4], and Ph3GeH in the ionic liquid [BMIm][NTf2]. [Mn(CO)6][AlCl4] and triphenylgermane turn out to be essential as reactive carbonyl precursors and for the reduction of GeI4. According to X-ray structure analysis based on single crystals, the title compound exhibits a novel MnGe3 cluster unit with Mn-Ge single bonds and surprisingly short distances (236-241 pm). Although sensitive to oxygen/moisture, the carbonyl compound is stable up to a temperature of 150 °C. Mass spectrometry (MS) shows [Mn(CO)3(GeI3)2]-, [Mn(CO)3(GeI3)I]-, and [GeI3]- as decomposition fragments in the gas phase. In addition to crystal structure analysis and MS, the title compound is characterized by energy-dispersive X-ray spectroscopy (EDXS), thermogravimetry (TG), optical spectroscopy (UV-visible), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations.Silica-coated nanoparticles are widely used in biomedical applications such as theranostics, imaging, and drug delivery. While silica-coated nanoparticles are biocompatible, experimental evidence shows that they can trigger innate immune reactions, and a broader understanding of what types of reactions are caused and how to mitigate them is needed. Herein, we investigated how the noncovalent surface functionalization of silica nanoparticles with purified proteins can inhibit nanoparticle-induced complement activation and macrophage uptake, two of the most clinically relevant innate immune reactions related to nanomedicines. Silica nanoparticles were tested alone and after coating with bovine serum albumin, human serum albumin, fibrinogen, complement factor H (FH), or immunoglobulin G (IgG) proteins. Enzyme-linked immunosorbent assays measuring the generation of various complement activation products indicated that silica nanoparticles induce complement activation via the alternative pathway. All protein coatings other than IgG protected against complement activation to varying extents. Most proteins acted as steric blockers to inhibit complement protein deposition on the nanoparticle surface, while FH coatings were biologically active and inhibited a key step in the amplification loop of complement activation, as confirmed by Western blot analysis. Flow cytometry and fluorescence microscopy experiments further revealed that complement activation-inhibiting protein coatings blunted macrophage uptake as well. Taken together, our findings demonstrate a simple and effective way to coat silica nanoparticles with purified protein coatings in order to mitigate innate immune reactions. Such methods are readily scalable and might constitute a useful strategy for improving the immunological safety profile of silica and silica-coated nanoparticles as well as other types of inorganic nanoparticles.