Johanssonfrancis3722

Preliminary mechanistic experiments reveal that a 'Cu-CF3' species is formed during this process and the critical C(sp3)-CF3 bond-forming step involves the copper catalyst.Advances in chemical control of the photophysical properties of transition-metal complexes are revolutionizing a wide range of technologies, particularly photocatalysis and light-emitting diodes, but they rely heavily on molecules containing precious metals such as ruthenium and iridium. Although the application of earth-abundant 'early' transition metals in photosensitizers is clearly advantageous, a detailed understanding of excited states with ligand-to-metal charge transfer (LMCT) character is paramount to account for their distinct electron configurations. Here we report an air- and moisture-stable, visible light-absorbing Zr(IV) photosensitizer, Zr(MesPDPPh)2, where [MesPDPPh]2- is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. JAK activation This molecule has an exceptionally long-lived triplet LMCT excited state (τ = 350 μs), featuring highly efficient photoluminescence emission (Ф = 0.45) due to thermally activated delayed fluorescence emanating from the higher-lying singlet configuration with significant LMCT contributions. Zr(MesPDPPh)2 engages in numerous photoredox catalytic processes and triplet energy transfer. Our investigation provides a blueprint for future photosensitizer development featuring early transition metals and excited states with significant LMCT contributions.Ionic conductors serve as solid electrolytes for fuel cells and batteries, whereas polar crystals such as ferroelectrics and pyroelectrics-which are typically insulating materials-are used in electronic devices. Here we show a material that combines superionic conductivity with a polar crystal structure at room temperature. This three-dimensional anionic network is based on -Fe-N≡C-Mo- units, with Cs cations hosted in every other pore. In the resulting Cs1.1Fe0.95[Mo(CN)5(NO)]·4H2O material, the negative and positive charges of the framework and Cs+ ions, respectively, are non-symmetrically shifted in the c-axis direction of the unit cell, and spontaneous electric polarization is generated, in turn leading to second harmonic generation (SHG). Additionally, this material is a superionic conductor (with an ionic conductivity value of 4 × 10-3 S cm-1 at 318 K). Furthermore, the ionic conductivity significantly decreases under 532 nm light irradiation (from 1 × 10-3 S cm-1 to 6 × 10-5 S cm-1 at room temperature) and, when irradiation stops, returns to its original value within ~1 h.Electronic symmetry breaking by charge disproportionation results in multifaceted changes in the electronic, magnetic and optical properties of a material, triggering ferroelectricity, metal/insulator transition and colossal magnetoresistance. Yet, charge disproportionation lacks technological relevance because it occurs only under specific physical conditions of high or low temperature or high pressure. Here we demonstrate a voltage-triggered charge disproportionation in thin molecular films of a metal-organic complex occurring in ambient conditions. This provides a technologically relevant molecular route for simultaneous realization of a ternary memristor and a binary memcapacitor, scalable down to a device area of 60 nm2. Supported by mathematical modelling, our results establish that multiple memristive states can be functionally non-volatile, yet discrete-a combination perceived as theoretically prohibited. Our device could be used as a binary or ternary memristor, a binary memcapacitor or both concomitantly, and unlike the existing 'continuous state' memristors, its discrete states are optimal for high-density, ultra-low-energy digital computing.Lysosomes have become an important target for anticancer therapeutics because lysosomal cell death bypasses the classical caspase-dependent apoptosis pathway, enabling the targeting of apoptosis- and drug-resistant cancers. However, only a few small molecules-mostly repurposed drugs-have been tested so far, and these typically exhibit low cancer selectivity, making them suitable only for combination therapies. Here, we show that mixed-charge nanoparticles covered with certain ratios of positively and negatively charged ligands can selectively target lysosomes in cancerous cells while exhibiting only marginal cytotoxicity towards normal cells. This selectivity results from distinct pH-dependent aggregation events, starting from the formation of small, endocytosis-prone clusters at cell surfaces and ending with the formation of large and well-ordered nanoparticle assemblies and crystals inside cancer lysosomes. These assemblies cannot be cleared by exocytosis and cause lysosome swelling, which gradually disrupts the integrity of lysosomal membranes, ultimately impairing lysosomal functions and triggering cell death.Defining the risks associated with diabetes mellitus in patients undergoing penile prosthesis implantation remains controversial. Our study aims to assess whether preoperative hemoglobin a1c and preoperative blood glucose levels are associated with an increased risk for postoperative infection in diabetic men. We performed a retrospective review of 932 diabetic patients undergoing primary penile prosthesis implantation from 18 high-volume penile prosthesis implantation surgeons throughout the United States, Germany, Belgium, and South Korea. Preoperative hemoglobin a1c and blood glucose levels within 6 h of surgery were collected and assessed in univariate and multivariate models for correlation with postoperative infection, revision, and explantation rates. The primary outcome is postoperative infection and the secondary outcomes are postoperative revision and explantation. In all, 875 patients were included in the final analysis. There were no associations between preoperative blood glucose levels or hemoglobin a1c levels and postoperative infection rates; p = 0.220 and p = 0.598, respectively. On multivariate analysis, a history of diabetes-related complications was a significant predictor of higher revision rates (p = 0.034), but was nonsignificant for infection or explantation rates. We conclude preoperative blood glucose levels and hemoglobin a1c levels are not associated with an increased risk for postoperative infection, revision, or explantation in diabetic men undergoing penile prosthesis implantation.