Environmental Control of Triplet Emission in Donor–Bridge–Acceptor Organometallics

Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.     

Helium droplet assisted synthesis of plasmonic Ag@ZnO core@shell nanoparticles

Plasmonic Ag@ZnO core@shell nanoparticles are formed by synthesis inside helium droplets with subsequent deposition and controlled oxidation. The particle size and shape can be controlled from spherical sub-10 nm particles to larger elongated structures. An advantage of the method is the complete absence of solvents, precursors, and other chemical agents. The obtained particle morphology and elemental composition have been analyzed by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS). The results reveal that the produced particles form a closed and homogeneous ZnO layer around a 2–3 nm Ag core with a uniform thickness of (1.33 ± 0.15) nm and (1.63 ± 0.31) nm for spherical and wire-like particles, respectively. The results are supported by ultraviolet photoelectron spectroscopy (UPS), which indicates a fully oxidized shell layer for the particles studied by STEM. The plasmonic properties of the produced spherical Ag@ZnO core@shell particles are investigated by two-photon photoelectron (2PPE) spectroscopy. Upon excitation of the localized surface plasmon resonance in Ag at around 3 eV, plasmonic enhancement leads to the liberation of electrons with high kinetic energy. This is observed for both Ag and Ag@ZnO particles, showing that even if a Ag cluster is covered by the ZnO layer, a plasmonic enhancement can be observed by photoelectron spectroscopy.

     

Optimizing PSMA Radioligand Therapy for Patients with Metastatic Castration-Resistant Prostate Cancer. A Systematic Review and Meta-Analysis

The aim of the review was to evaluate patient and treatment characteristics for patients with metastatic castration-resistant prostate cancer (mCRPC) treated with PSMA radioligand therapy (PRLT) associated with above-average outcome. The systematic review and meta-analysis followed recommendations by the Preferred Reporting Items for Systematic reviews and Meta-Analysis (PRISMA). We searched for publications in PubMed, Embase, and ClinicalTrials.gov up to 31 September 2020. Thirty-six publications and four duplicates reported 2346 patients. Nearly two-thirds of the patients had bone metastases. Median overall survival (OS) was 16 months. Asymptomatic patients and patients with only lymph node metastases lived longer than symptomatic patients and patients with more extensive metastases. Patients treated with an intensified schedule of ¹⁷⁷Lu PRLT lived longer than those treated with a conventional schedule. Half of the patients obtained a PSA decline ≥ 50% and these patients lived longer than those with less PSA decline. Approximately 10% of the patients developed hematologic toxicity with anemia grade 3 as the most severe adverse effect. Characteristics for patients, cancer, restaging, and PRLT predict above average overall survival following treatment with PRLT.     

Some Molecular and Cellular Stress Mechanisms Associated with Neurodegenerative Diseases and Atherosclerosis

Chronic stress is a combination of nonspecific adaptive reactions of the body to the influence of various adverse stress factors which disrupt its homeostasis, and it is also a corresponding state of the organism’s nervous system (or the body in general). We hypothesized that chronic stress may be one of the causes occurence of several molecular and cellular types of stress. We analyzed literary sources and considered most of these types of stress in our review article. We examined genes and mutations of nuclear and mitochondrial genomes and also molecular variants which lead to various types of stress. The end result of chronic stress can be metabolic disturbance in humans and animals, leading to accumulation of reactive oxygen species (ROS), oxidative stress, energy deficiency in cells (due to a decrease in ATP synthesis) and mitochondrial dysfunction. These changes can last for the lifetime and lead to severe pathologies, including neurodegenerative diseases and atherosclerosis. The analysis of literature allowed us to conclude that under the influence of chronic stress, metabolism in the human body can be disrupted, mutations of the mitochondrial and nuclear genome and dysfunction of cells and their compartments can occur. As a result of these processes, oxidative, genotoxic, and cellular stress can occur. Therefore, chronic stress can be one of the causes forthe occurrence and development of neurodegenerative diseases and atherosclerosis. In particular, chronic stress can play a large role in the occurrence and development of oxidative, genotoxic, and cellular types of stress.     

Modeling the Electrical Conductive Paths within All-Solid-State Battery Electrodes

All-solid-state batteries constitute a very promising energy storage device. Two very important properties of these battery cells are the ionic and the electrical conductivity, which describe the ion and the electron transport through the electrodes, respectively. In this work, a numerical method is presented to model the electrical conductivity, considering the outcome of discrete-element method simulations and the intrinsic conductivities of both the active material particles and the conductive additive particles. The results are calibrated and validated with the help of experimental data of real manufactured electrodes. The tortuosity, which strongly influences the ionic conductivity, is also presented for the analyzed electrodes, taking their microstructure into account.     

Influence of Macromolecular Brushes with Polyimide Backbones and Poly(methyl methacrylate) Side Chains on Structure,Physical, and Transport Properties of Polyphthalamide

Composite films based on polyamide (poly(m-phenylene-iso-phthalamide)) (PA) and a brush-like polymer with polyimide (PI) backbone and side poly(methyl methacrylate) chains (PI-PMMA) were prepared by mixing individual solutions of PA and PI-PMMA and subsequent film casting. Macromolecular brushes with the same backbone length and density of side chains but with various lengths of side PMMA chains were synthesized via activator generated by electron transfer atom transfer radical polymerization. Interactions between PA and PI-PMMA, as well as distribution of PI-PMMA filler inside the PA matrix, were studied by viscometry, dynamic light scattering, differential scanning calorimetry, scanning electron microscopy, and IR spectroscopy. The mechanical properties of polymer samples were also investigated. Microphase separation was revealed in PA/PI-PMMA films. The length of side chains influences interactions between PA and PI-PMMA. At the same time, the degree of reduction in the rigidity parameters and in the elasticity parameter depends on the side chain length. Diffusion membranes were prepared on the basis of compositions with the best mechanical properties; these membranes proved to be highly efficient in pervaporation of methanol–hexane mixture. It was established that the fluxes and separation factors of the studied membranes are several times higher as compared to the corresponding characteristics of known commercial membranes. POLYM. ENG. SCI., 60:481–490, 2020. © 2019 Society of Plastics Engineers     

Predicting the damage development in epoxy resins using an anisotropic damage model

For fiber-reinforced plastics, the strain-rate dependent response is governed by the matrix behavior. In this work, the Goldberg model is considered for the epoxy matrix constitutive material model. Moreover, the strain-rate dependency is achieved by direct influence on the elastic modulus, the inelastic strain, and the material strain to failure. In addition, an anisotropic damage response is implemented and extended through a strain-rate dependent definition. Since the constitutive model relies on nonphysical parameters, a parameter study is further performed. Additional numerical investigations using a micro-mechanical model are performed. Tension and shear loading conditions are evaluated and the influence of different strain rates is explored. Furthermore, the implemented anisotropic damage model is compared and discussed against an isotropic damage model.