Ballingovesen6679

Gold(III) complexes are versatile catalysts offering a growing number of new synthetic transformations. Our current understanding of the mechanism of homogeneous gold(III) catalysis is, however, limited, with that of phosphorus-containing complexes being hitherto underexplored. The ease of phosphorus oxidation by gold(III) has so far hindered the use of phosphorus ligands in the context of gold(III) catalysis. We present a method for the generation of P,N-chelated gold(III) complexes that circumvents ligand oxidation and offers full counterion control, avoiding the unwanted formation of AuCl4-. On the basis of NMR spectroscopic, X-ray crystallographic, and density functional theory analyses, we assess the mechanism of formation of the active catalyst and of gold(III)-mediated styrene cyclopropanation with propargyl ester and intramolecular alkoxycyclization of 1,6-enyne. P,N-chelated gold(III) complexes are demonstrated to be straightforward to generate and be catalytically active in synthetically useful transformations of complex molecules.The limitation on signal processes implementable using conventional semiconductor circuits based on electric signals necessitates a revolutionary change in device structures such that they can exploit photons or light. Herein, we introduce optoelectric logic circuits that convert optical signals with different wavelengths corresponding to different colors into binary electric signals. Such circuits are assembled using unit devices in which the electric current through the semiconductor channel is effectively gated by lights of different colors. Color-selective optical modulation of the device is cleverly achieved using graphene decorated with different organic dyes as the electrode of a Schottky diode structure. The drastic change in the electrode work function under illumination induces a change in the height of the Schottky barrier formed at the electrode/semiconductor junction and consequent modulation of the electric current; we term the developed device a photonic barristor. We construct logic circuits using an array of photonic barristors and demonstrate that they execute the functions of conventional NAND and NOR gates from optical input signals.Flucloxacillin is a β-lactam antibiotic associated with a high incidence of drug-induced liver reactions. Although expression of HLA-B*5701 increases susceptibility, little is known about the pathological mechanisms involved in the induction of the clinical phenotype. Irreversible protein modification is suspected to drive the reaction through the presentation of flucloxacillin-modified peptides by the risk allele. In this study, the binding of flucloxacillin to proteins of liver-like cells was characterized. Flucloxacillin was shown to bind to proteins localized in bile canaliculi regions, coinciding with the site of clinical disease. The localization of flucloxacillin was mediated primarily by the membrane transporter multidrug resistance-associated protein 2. Modification of multiple proteins by flucloxacillin in bile canaliculi regions may provide a potential local source of neo-antigens for HLA presentation in the liver.Cities are responsible for more than 80% of global greenhouse gas emissions. Sequestration of air pollutants is one of the main ecosystem services that urban forests provide to the citizens. The atmospheric concentration of several pollutants such as carbon dioxide (CO2), tropospheric ozone (O3), and particulate matter (PM) can be reduced by urban trees through processes of adsorption and deposition. We predict the quantity of CO2, O3, and PM removed by urban tree species with the multilayer canopy model AIRTREE in two representative urban parks in Italy Park of Castel di Guido, a 3673 ha reforested area located northwest of Rome, and Park of Valentino, a 42 ha urban park in downtown Turin. We estimated a total annual removal of 1005 and 500 kg of carbon per hectare, 8.1 and 1.42 kg of ozone per hectare, and 8.4 and 8 kg of PM10 per hectare. We highlighted differences in pollutant sequestration between urban areas and between species, shedding light on the importance to perform extensive in situ measurements and modeling analysis of tree characteristics to provide realistic estimates of urban parks to deliver ecosystem services.Covalent organic framework (COF)-based membranes are burgeoning candidates for separation technologies owing to their well-ordered channel structures. The exponential interest in the stability of the COF membrane on exposure to harsh organic solvents is directed to develop a composite membrane for dye separations in polar aprotic solvents. Here, we reported a nanocomposite membrane composing of a single-walled carbon nanotube (SWCNT)/COF (an imine-based COF) hybrid on a commercial polytetrafluoroethylene (PTFE) substrate, with a thickness of ∼58 nm prepared in a diffusion cell. read more This membrane displayed high permeability and stability toward nonpolar and aprotic solvents. It exhibited high permeability for lower viscous organic solvents such as hexane (66 L m-2 h-1 bar-1), acetone (60 L m-2 h-1 bar-1), and acetonitrile (59 L m-2 h-1 bar-1) with a desirable dye rejection (92.8% for Brilliant blue in acetone). The long-time operation demonstrated the excellent stability of the nanocomposite membrane. We herein reported a facile and mild method to prepare an ultrathin COF-based nanocomposite membrane with a porous, robust structure coupled with solvent durability capable of efficient dye separation.Sweat sensors that can continuously sample sweat are critical for determining the time-dependent physiological responses occurring in normal daily life. Here, a new device, termed fluidic patch, for collecting human sweat samples at defined time intervals is developed, and the proof-of-concept is demonstrated. The device comprises micropumps and a disposable microfluidic patch attached to the human skin. The fluidic patch continuously collects aliquots of freshly secreted sweat accumulated in the fluidic pathway at accurately defined time windows (typically 5 min). By measuring the weight of the collected samples, the local sweat rate is calculated. The sweat sample collected can be directly subjected to a wide range of chemical analyses. For the proof-of-concept, we compared the sweat rates during passive heating in human trials using the fluidic patch and the conventional ventilated sweat capsule system. Although the sweat rate obtained using the fluidic patch highly correlated with that of the ventilated sweat capsule (R2 = 0.96, y = 1.4x - 0.05), the fluidic patch overestimated the sweat rate compared with the ventilated capsule system when the sweat rate exceeded 0.5 mg/(cm2·min). The sampled sweat was analyzed for sodium, potassium, chloride, lactate, pyruvate, and cortisol. The device could obtain the time courses of the concentrations of the abovementioned three ions; the concentrations of sodium and chloride increased linearly with the sweat rate during passive heating (R2 = 0.76 and 0.66, respectively). link2 The device can reliably measure the sweat rate and collect sweat samples for chemical analysis. It can be utilized for real-time physiological investigations toward wider applications.Iron-clay-cyclodextrin composites were designed as sorbent catalysts to adsorb and oxidize pollutants from water. The clay-iron backbone served as a mechanical support and as a heterogeneous Fenton catalyst, and the cyclodextrin monomers or polymers cross-linked with polyfluorinated aromatic molecules were used to accommodate adsorption of the pollutants. The composite based on iron-clay-cyclodextrin-polymers (Fe-MMT-βCD-DFB) exhibited superior adsorption and degradation of the model pollutants, bisphenol A (BPA), carbamazepine (CBZ), and perfluorooctanoic acid (PFOA), compared to the monomer-based composite and the native iron clay. The variety of adsorption sites, such as the polyfluorinated aromatic cross-linker, cyclodextrin toroid, and iron-clay surface, resulted in high adsorption affinity toward all pollutants; BPA was primarily adsorbed to the cyclodextrin functional groups, CBZ showed high affinity toward the Fe-MMT surface and the Fe-MMT-βCD-DFB composite, whereas PFOA was adsorbed mainly to the βCD-DFB polymer. Degradation, using H2O2, was highly efficient, reaching over 90% degradation in 1 h for BPA and CBZ and ∼80% for PFOA. The composite also showed excellent degradation efficiency in a multicomponent system with all three model pollutants. Furthermore, the composite's activity remained steady for five consecutive cycles of adsorption and degradation. The ability to remediate a broad range of pollutants, and the high overall removal exhibited by this novel material, demonstrates the potential for future application in water remediation technologies.Tumor-associated macrophages (TAMs), a major player in the tumor microenvironment, were recently recognized as a potential therapeutic target. To date, very few anticancer drugs or drug-delivery systems were designed to target the TAMs. Inspired by the "eat me" signal, phosphatidylserine (PS), mediated phagocytic clearance of apoptotic bodies, in this study, the matrix metalloproteinase 2 (MMP2)-sensitive PS-modified nanoparticles were developed. In the design, the PS is externalized to the nanoparticles' surface only when the nanoparticles reach the MMP2-overexpressing tumor site, allowing for the TAM-specific phagocytosis. The nanoparticles' excellent macrophage/TAM selectivity was observed in various biological models, including various cell lines, coculture cells, coculture cell spheroids, zebrafish, and tumor-bearing mice. The nanoparticles' TAM specificity remarkably enhanced the TAM depletion capability of the loaded model drug, dasatinib, resulting in the improved anticancer activity. link3 The MMP2-sensitive apoptotic body-mimicking nanoparticles might be a promising delivery tool for TAM-centered cancer diagnoses and treatments.An impurity doping in semiconductors is an important irreversible process of manipulating the electrical properties of advanced electron devices. Here, we report an unusual reversible dopant activation/deactivation phenomenon, which emerges at an interface between indium tin oxide (ITO) and single-crystalline oxide channel. We found that the interface electrical resistance between ITO electrodes and single-crystalline oxide nanowire channel can be repeatedly switched between a metallic state and a near-insulative state by applying thermal treatments in air or vacuum. Interestingly, this electrical switching phenomenon disappears when the oxide nanowire changes from the single-crystalline structure to the lithography-defined polycrystalline structure. Atmosphere-controlled annealing experiments reveal that atmospheric oxygen induces repeatable change in the interfacial electrical resistance. Systematic investigations on metal cation species and channel crystallinity demonstrate that the observed electrical switching is related to an interface-specific reversible Sn-dopant activation/deactivation of ITO electrode in contact with a single-crystalline oxide channel.The exploration of ternary Pt-based catalysts represents a new trend for the application of electrocatalysts in fuel cells. In the present study, intermetallic PtPbBi hexagonal nanoplates (HNPs) with a hexagonal close-packed structure have been successfully synthesized via a facile solvothermal synthesis approach. The optimized PtPbBi HNPs exhibited excellent mass activity in the ethanol oxidation reaction (8870 mA mg-1Pt) in an alkaline ethanol solution, which is 12.7 times higher than that of JM Pt/C. Meanwhile, the mass activity of PtPbBi HNPs in an ethylene glycol solution (10,225 mA mg-1Pt) is 1.85 times higher than that of JM Pt/C. In particular, its catalytic activity is better than that of most reported Pt-based catalysts. In addition, the optimized PtPbBi HNPs also show a better operational durability than commercial Pt/C. For the ethylene glycol oxidation reaction, a mass activity of 42.7% was retained even after a chronoamperometric test for 3600 s, which is rare among the reported Pt-based catalysts.