TADF Blue Emitters with Balanced π-Conjugation─Design, Synthesis, Spectral Characterization, and a Model OLED with 8-(5-(tert-Butyl)-1,3,4-oxadiazol-2-yl)-N,N-bis(4-(tert-butyl)phenyl)dibenzo[b,d]furan-2-amine.

Blue organic light-emitting diodes (OLED) suffer from relatively short lifetimes and a comparatively low lighting efficiency. One of the approaches to improving their characteristics is the development of luminophores with the potential for thermally activated delayed fluorescence (TADF). Herein, a set of donor-spacer-acceptor compounds with potential for TADF are designed, synthesized, and computationally and spectroscopically characterized. The excited state dynamics of the most prospective dye is monitored by time-resolved fluorescence and transient absorption spectroscopy. The experimental data are obtained and processed by a newly developed method and supplemented by quantum chemical calculations. The comprehensive approach allowed rationalization of the complex cascade-type photophysical behavior. The most promising emitter is included in an OLED displaying a blue color with a maximum EQE of 4.9% and negligible efficiency roll-off at higher luminance.

Drug-associated acquired hemophilia A: an analysis based on 185 cases from the WHO pharmacovigilance database.

INTRODUCTION: Acquired hemophilia A (AHA) is a rare autoimmune hemorrhagic disease occurring in several underlying conditions. Drug-associated AHA (D-AHA) is poorly addressed nowadays. AIM: This work aims to identify and characterize which drugs are associated with AHA using the WHO global database of reported potential effects of medicinal products (VigiBase). METHODS: First, we realized a disproportionality analysis using the information component (IC) to identify D-AHA in VigiBase. IC compares observed- and expected-values in order to find associations between drugs and adverse drug reactions (ADRs) using disproportionate Bayesian reporting. IC025 is the lower end of a 95% credibility interval for the IC. Then, we collected cases of drugs significantly associated with AHA from July 2004 to November 2021. RESULTS: 14 drugs with IC025 > 0 were identified representing a total of 185 cases. D-AHA occurred more frequently in men (59%) than women (41%). The median (min-max) age at onset was 75 years (8-98). The median [Q1-Q3] time to onset of D-AHA from the start of the suspected drug was 30 days [9.5-73.75] and 10% of cases resulted in a fatality. The drugs associated with the highest IC025 (IC025 > 2) were Clopidogrel, Alemtuzumab, Omalizumab. This study retrieved for the first time three usually used drugs (3/14) that exhibit a significant pharmacovigilance signal for D-AHA. CONCLUSION: This worldwide pharmaco-epidemiologic study updates the list of the drugs associated with AHA. The clinician should be aware of these possible severe ADR, which might require larger epidemiological and pathophysiologic studies.

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters.

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.

Evolutionary Approach to Biological Homochirality.

We study a very simple linear evolutionary model based on distribution of protocells by total enantiomeric excess and without any mutual inhibition and show that such model can produce two species with values of total enantiomeric excess in each of the species approaching [Formula: see text] when there is a global [Formula: see text] symmetry. We then consider a scenario when there is a small external global asymmetry factor, like weak interaction, and show that only one of the species remains in such a case, and that is the one, which is more efficient in replication. We perform an estimate of the time necessary to reach homochirality in such a model and show that reasonable assumptions lead to an estimate of around 300 thousand years plus or minus a couple of orders of magnitude. Despite this seemingly large time to reach homochirality, the model is immune to racemization because amino acids in the model follow the lifespan of the protocells rather than the time needed to reach homochirality. We show that not needing mutual inhibition in such evolutionary model is due to the difference in the topology of the spaces in which considered model and many known models of biological homochirality operate. Bifurcation-based models operate in disconnected zero-dimensional space (the space is just two points with enantiomeric excess equal [Formula: see text] and [Formula: see text]), whereas considered evolutionary model (in its continuous representation) operates in one-dimensional connected space, that is the whole interval between [Formula: see text] and [Formula: see text] of total enantiomeric excess. We then proceed with the analysis of the replication process in non-homochiral environment and show that replication errors (the probability to attach an amino acid of wrong chirality) result in a smooth decrease of replication time when total enantiomeric excess of the replicated structure moves away from zero. We show that this decrease in replication time is sufficient for considered model to work.

Porous carbon architectures with different dimensionalities for lithium metal storage.

Lithium metal batteries have recently gained tremendous attention owing to their high energy capacity compared to other rechargeable batteries. Nevertheless, lithium (Li) dendritic growth causes low Coulombic efficiency, thermal runaway, and safety issues, all of which hinder the practical application of Li metal as an anodic material. In this review, the failure mechanisms of Li metal anode are described according to its infinite volume changes, unstable solid electrolyte interphase, and Li dendritic growth. The fundamental models that describe the Li deposition and dendritic growth, such as the thermodynamic, electrodeposition kinetics, and internal stress models are summarized. From these considerations, porous carbon-based frameworks have emerged as a promising strategy to resolve these issues. Thus, the main principles of utilizing these materials as a Li metal host are discussed. Finally, we also focus on the recent progress on utilizing one-, two-, and three-dimensional carbon-based frameworks and their composites to highlight the future outlook of these materials.

Li2 S-Based Li-Ion Sulfur Batteries: Progress and Prospects.

The great demand for high-energy-density batteries has driven intensive research on the Li-S battery due to its high theoretical energy density. Consequently, considerable progress in Li-S batteries is achieved, although the lithium anode material is still challenging in terms of lithium dendrites and its unstable interface with electrolyte, impeding the practical application of the Li-S battery. Li2 S-based Li-ion sulfur batteries (LISBs), which employ lithium-metal-free anodes, are a convenient and effective way to avoid the use of lithium metal for the realization of practical Li-S batteries. Over the past decade, studies on LISBs are carried out to optimize their performance. Herein, the research progress and challenges of LISBs are reviewed. Several important aspects of LISBs, including their working principle, the physicochemical properties of Li2 S, Li2 S cathode material composites, LISBs full batteries, and electrolyte for Li2 S cathode, are extensively discussed. In particular, the activation barrier in the initial charge process is fundamentally analyzed and the mechanism is discussed in detail, based on previous reports. Finally, perspectives on the future direction of the research of LISBs are proposed.

The Dual Functions of Defect-Rich Carbon Nanotubes as Both Conductive Matrix and Efficient Mediator for LiS Batteries.

LiS batteries are considered a promising energy storage system owing to the great abundance of sulfur and its high specific capacity. Polysulfide shuttling and sluggish reaction kinetics in sulfur cathodes significantly degrade the cycle life of LiS batteries. A modified method is employed to create defects in carbon nanotubes (CNTs), anchoring polysulfides, and accelerating electrochemical reactions. The defect-rich CNTs (D-CNT) enable dramatic improvement in both cycling and rate performance. A specific capacity of 600 mAh g-1 with a current density of 0.5 C is achieved after 400 cycles, and even at a very high current density (5.0 C), a specific capacity of 434 mAh g-1 is observed. Cycling stability up to 1000 cycles is also achieved under the conditions of high sulfur loading and lean electrolyte. Theoretical calculations revealed that the improvement is mainly attributable to the electronic structure of defect-rich carbon, which has higher binding energy with polysulfides because of the upshift of the p-band center. Furthermore, rotating disk electrode measurements demonstrate that the defect-rich carbon can accelerate the polysulfide conversion process. It is anticipated that this new design strategy can be the starting point for mediator-like carbon materials with good conductivity and high catalytic activity for LiS batteries.

Chiral Symmetry Breaking in Large Peptide Systems.

Chiral symmetry breaking in far from equilibrium systems with large number of amino acids and peptides, like a prebiotic Earth, was considered. It was shown that if organic catalysts were abundant, then effective averaging of enantioselectivity would prohibit any symmetry breaking in such systems. It was further argued that non-linear (catalytic) reactions must be very scarce (called the abundance parameter) and catalysts should work on small groups of similar reactions (called the similarity parameter) in order to chiral symmetry breaking have a chance to occur. Models with 20 amino acids and peptide lengths up to three were considered. It was shown that there are preferred ranges of abundance and similarity parameters where the symmetry breaking can occur in the models with catalytic synthesis / catalytic destruction / both catalytic synthesis and catalytic destruction. It was further shown that models with catalytic synthesis and catalytic destruction statistically result in a substantially higher percentage of the models where the symmetry breaking can occur in comparison to the models with just catalytic synthesis or catalytic destruction. It was also shown that when chiral symmetry breaking occurs, then concentrations of some amino acids, which collectively have some mutually beneficial properties, go up, whereas the concentrations of the ones, which don't have such properties, go down. An open source code of the whole system was provided to ensure that the results can be checked, repeated, and extended further if needed.

Nano-sunscreens - a double-edged sword in protecting consumers from harm: viewing Australian regulatory policies through the lenses of the European Union.

Nanotechnology has the potential to bring about revolutionary changes in manufacturing products, including sunscreens. However, a knowledge gap between benefits and detriments of engineered nano-materials used in sunscreens exists, which gives rise to safety concerns. This article is concerned with the protection of consumers without impairing the embellishment of this promising technology. It is widely argued that the harm associated with nano-sunscreens may only occur under certain conditions related mainly to users skin vulnerability, which can be avoided by informed and careful use of such a product. We thus recognize the need for fostering the growth of nanotech simultaneously with preventing potential harm. We revisit the Australian sunscreens regulatory policies, which embrace a "wait and see" approach, through the lens of regulatory policies in the European Union (EU) that are influenced by a "precautionary principle." We highlight the importance of informing consumers about the sunscreen they are using and recommend that product labels should disclose the presence of nano-ingredients in line with the EU disclosure requirements. This will allow users to carefully apply the product in order to avoid any potential harm and to protect manufacturers from possible costly litigation in future. This can be achieved through a combined collaborative effort of regulators, supply chain entities, and end users.

Tuning Wall Thicknesses in Mesoporous Silica Films for Optimization of Optical Anti-Reflective Properties.

This work reports the fabrication of mesoporous silica films with controllable wall thicknesses by spin coating of precursor solutions consisting of polystyrene-block-polybutadiene-block-polystyrene based triblock copolymers (Hydrogenated methyl Styrene Ethylene Butadiene methyl Styrene, HmSEBmS) and tetraethyl orthosilicate (TEOS) followed by calcination in air at 600 °C, for optical anti-reflection films. By changing the relative weight of the triblock polymer to TEOS, the pore-to-pore distance in the mesoporous silica film can be controlled without significantly affecting the size of the mesopores, thus, enabling effective control of the refractive index and porosity of the films. In terms of optical properties, the transmittance of the fabricated mesoporous silica film is approximately 3.3% higher than that of the uncoated glass substrate in the wavelength range of 400 to 750 nm.

Chiral Symmetry Breaking in Peptide Systems During Formation of Life on Earth.

Chiral symmetry breaking in complex chemical systems with a large number of amino acids and a large number of similar reactions was considered. It was shown that effective averaging over similar reaction channels may result in very weak effective enantioselectivity of forward reactions, which does not allow most of the known models to result in chiral symmetry breaking during formation of life on Earth. Models with simple and catalytic synthesis of a single amino acid, formation of peptides up to length five, and sedimentation of insoluble pair of substances were considered. It was shown that depending on the model and the values of the parameters, chiral symmetry breaking may occur in up to about 10% out of all possible unique insoluble pair combinations even in the absence of any catalytic synthesis and that minimum total number of amino acids in the pair is 5. If weak enantioselective forward catalytic synthesis of amino acids is present, then the number of possible variants, in which chiral symmetry breaking may occur, increases substantially. It was shown that that the most interesting catalysts have zero or one amino acid of "incorrect" chirality. If the parameters of the model are adjusted in such a way to result in an increase of concentration of longer peptides, then catalysts with two amino acids of incorrect chirality start to appear at peptides of length five. Models of chiral symmetry breaking in the presence of epimerization were considered for peptides up to length three. It was shown that the range of parameters in which chiral symmetry breaking could occur significantly shrinks in comparison to previously considered models with peptides up to length two. An experiment of chiral symmetry breaking was proposed. The experiment consists of a three-step cycle: reversible catalytic synthesis of amino acids, reversible synthesis of peptides, and irreversible sedimentation of insoluble substances.

A Facile Synthesis of High-Surface-Area Sulfur-Carbon Composites for Li/S Batteries.

Small-grained elemental sulfur is precipitated from sodium thiosulfate (Na2 S2 O3 ) in a carbon-containing oxalic acid (HOOC-COOH) solution through a novel spray precipitation method. Surface area analysis, elemental mapping, and transmission electron micrographs revealed that the spray-precipitated sulfur particles feature 11 times higher surface area compared to conventional precipitated sulfur, with homogeneous distribution in the carbon. Moreover, the scanning electron micrographs show that these high-surface-area sulfur particles are firmly adhered to and covered by carbon. This precipitated S-C composite exhibits high discharge capacity with about 75 % capacity retention. The initial discharge capacity was further improved to 1444 mA h g(-1) by inserting a free-standing single-walled carbon nanotube layer in between the cathode and the separator. Moreover, with the help of the fixed capacity charging technique, 91.6 % capacity retention was achieved.

International recommendations for the assessment of autoantibodies to cellular antigens referred to as anti-nuclear antibodies.

Anti-nuclear antibodies (ANA) are fundamental for the diagnosis of autoimmune diseases, and have been determined by indirect immunofluorescence assay (IIFA) for decades. As the demand for ANA testing increased, alternative techniques were developed challenging the classic IIFA. These alternative platforms differ in their antigen profiles, sensitivity and specificity, raising uncertainties regarding standardisation and interpretation of incongruent results. Therefore, an international group of experts has created recommendations for ANA testing by different methods. Two groups of experts participated in this initiative. The European autoimmunity standardization initiative representing 15 European countries and the International Union of Immunologic Societies/World Health Organization/Arthritis Foundation/Centers for Disease Control and Prevention autoantibody standardising committee. A three-step process followed by a Delphi exercise with closed voting was applied. Twenty-five recommendations for determining ANA (1-13), anti-double stranded DNA antibodies (14-18), specific antibodies (19-23) and validation of methods (24-25) were created. Significant differences between experts were observed regarding recommendations 24-25 (p<0.03). Here, we formulated recommendations for the assessment and interpretation of ANA and associated antibodies. Notably, the roles of IIFA as a reference method, and the importance of defining nuclear and cytoplasmic staining, were emphasised, while the need to incorporate alternative automated methods was acknowledged. Various approaches to overcome discrepancies between methods were suggested of which an improved bench-to-bedside communication is of the utmost importance. These recommendations are based on current knowledge and can enable harmonisation of local algorithms for testing and evaluation of ANA and related autoantibodies. Last but not least, new more appropriate terminologies have been suggested.

Multifunctional Separator Enables High-Performance Sodium Metal Batteries in Carbonate-Based Electrolytes.

Sodium metal has become one of the most promising anodes for next-generation cheap and high-energy-density metal batteries; however, challenges caused by the uncontrollable sodium dendrite growth and fragile solid electrolyte interphase (SEI) restrict their large-scale practical applications in low-cost and wide-voltage-window carbonate electrolytes. Herein, a novel multifunctional separator with lightweight and high thinness is proposed, assembled by the cobalt-based metal-organic framework nanowires (Co-NWS), to replace the widely applied thick and heavy glass fiber separator. Benefitting from its abundant sodiophilic functional groups and densely stacked nanowires, Co-NWS not only exhibits outstanding electrolyte wettability and effectively induces uniform Na+ ion flux as a strong ion redistributor but also favors constructing the robust N,F-rich SEI layer. Satisfactorily, with 10 µL carbonate electrolyte, a Na|Co-NWS|Cu half-cell delivers stable cycling (over 260 cycles) with a high average Coulombic efficiency of 98%, and the symmetric cell shows a long cycle life of more than 500 h. Remarkably, the full cell shows a long-term life span (over 1500 cycles with 92% capacity retention) at high current density in the carbonate electrolyte. This work opens up a strategy for developing dendrite-free, low-cost, and long-life-span sodium metal batteries in carbonate-based electrolytes.

Low-Overpotential Rechargeable Na-CO2 Batteries Enabled by an Oxygen-Vacancy-Rich Cobalt Oxide Catalyst.

Rechargeable sodium-carbon dioxide (Na-CO2) batteries have been proposed as a promising CO2 utilization technique, which could realize CO2 reduction and generate electricity at the same time. They suffer, however, from several daunting problems, including sluggish CO2 reduction and evolution kinetics, large polarization, and poor cycling stability. In this study, a rambutan-like Co3O4 hollow sphere catalyst with abundant oxygen vacancies was synthesized and employed as an air cathode for Na-CO2 batteries. Density functional theory calculations reveal that the abundant oxygen vacancies on Co3O4 possess superior CO2 binding capability, accelerating CO2 electroreduction, and thereby improving the discharge capacity. In addition, the oxygen vacancies also contribute to decrease the CO2 decomposition free energy barrier, which is beneficial for reducing the overpotential further and improving round-trip efficiency. Benefiting from the excellent catalytic ability of rambutan-like Co3O4 hollow spheres with abundant oxygen vacancies, the fabricated Na-CO2 batteries exhibit extraordinary electrochemical performance with a large discharge capacity of 8371.3 mA h g-1, a small overpotential of 1.53 V at a current density of 50 mA g-1, and good cycling stability over 85 cycles. These results provide new insights into the rational design of air cathode catalysts to accelerate practical applications of rechargeable Na-CO2 batteries and potentially Na-air batteries.

Emerging Applications and Regulatory Strategies for Advanced Medicines Manufacturing - Towards the Development of a Platform Approach.

The last decade has seen Advanced Medicines Manufacturing (AMM) progress from isolated product developments to the creation of industry-academic centres of excellence, regulatory innovation progressing leading to new standards, and product commercialisation across multiple product formats. This paper examines these developments focusing on successful applications and strategies presented at the 2023 Symposium of the International Consortium for Advanced Medicines Manufacturing (ICAMM). Despite these exemplar applications, there remain significant challenges to the sector-wide adoption of AMM technologies. Drawing on Symposium delegate expert responses to open-ended questions, our coding-based thematic analysis suggest three primary enablers drive successful adoption of AMM technologies at scale, namely: the ability to leverage pre-competitive collaborations to challenge-based problem solving; information and knowledge sharing through centres of excellence; and the development of AMM specific regulatory standards. Further analysis of expert responses identified the emergence of a 'Platform creation' approach to AMM innovation; characterised by: i) New collaboration modes; ii) Exploration of common product-process platforms for new dosage forms and therapy areas; iii) Development of modular equipment assets that enable scale-out, and offer more decentralized or distributed manufacturing models; iv) Standards based on product-process platform archetypes; v) Implementation strategies where platform-thinking and AMM technologies can significantly reduce timelines between discovery, approval and GMP readiness. We provide a definition of the Platform creation concept for AMM and discuss the requirements for its systematic development.

Linearly Interlinked Fe-Nx-Fe Single Atoms Catalyze High-Rate Sodium-Sulfur Batteries.

Linearly interlinked single atoms offer unprecedented physiochemical properties, but their synthesis for practical applications still poses significant challenges. Herein, linearly interlinked iron single-atom catalysts that are loaded onto interconnected carbon channels as cathodic sulfur hosts for room-temperature sodium-sulfur batteries are presented. The interlinked iron single-atom exhibits unique metallic iron bonds that facilitate the transfer of electrons to the sulfur cathode, thereby accelerating the reaction kinetics. Additionally, the columnated and interlinked carbon channels ensure rapid Na+ diffusion kinetics to support high-rate battery reactions. By combining the iron atomic chains and the topological carbon channels, the resulting sulfur cathodes demonstrate effective high-rate conversion performance while maintaining excellent stability. Remarkably, even after 5000 cycles at a current density of 10 A g-1, the Na-S battery retains a capacity of 325 mAh g-1. This work can open a new avenue in the design of catalysts and carbon ionic channels, paving the way to achieve sustainable and high-performance energy devices.

CuS nanoflakes, microspheres, microflowers, and nanowires: synthesis and lithium storage properties.

CuS nanostructured materials, including nanoflakes, microspheres composed of nanoflakes, microflowers, and nanowires have been selectively synthesized by a facile hydrothermal method using CuSO4 and thiourea as precursors under different conditions. The morphology of CuS particles were affected by the following synthetic parameters: temperature, time, surfactant, pH value, solvent, and concentration of the two precursors. The synthesized CuS nanomaterials were characterized by X-ray diffraction, Brunauer-Emmett-Teller N2 adsorption, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The electrochemical tests, including constant current charge-discharge and cyclic voltammetry, show the specific capacities of the different morphologies, as well as their rate capability. The nanowire electrode has near theoretical specific capacity and the best rate capability.

Cerium oxide nanoparticles: influence of the high-Z component revealed on radioresistant 9L cell survival under X-ray irradiation.

This article pioneers a study into the influence of the high-Z component of nanoparticles on the efficacy of radioprotection some nanoparticles offer to exposed cells irradiated with X-rays. We reveal a significant decrease in the radioprotection efficacy for cells exposed to CeO2 nanoparticles and irradiated with 10 MV and 150 kVp X-rays. In addition, analysis of the 150 kVp survival curve data indicates a change in radiation quality, becoming more lethal for irradiated cells exposed to CeO2 nanoparticles. We attribute the change in efficacy to an increase in high linear energy transfer Auger electron production at 150 kVp which counterbalances the CeO2 nanoparticle radioprotection capability and locally changes the radiation quality. This study highlights an interesting phenomenon that must be considered if radiation protection drugs for use in radiotherapy are developed based on CeO2 nanoparticles. FROM THE CLINICAL EDITOR: CeO2 nanoparticles are thought to offer radioprotection; however, this study reveals significant decrease in the radioprotection efficacy for cells exposed to CeO2 nanoparticles and irradiated with 10 MV and 150 kVp X-rays. This phenomenon must be considered when developing radiation protection drugs based on CeO2 nanoparticles.

Multifunctional bismuth oxide (Bi2 O3 ) particles: Evidence for selective melanoma therapy.

The current study investigates the therapeutic and optical properties of bismuth oxide (Bi2 O3 ) particles for selective melanoma therapy and prevention. The Bi2 O3 particles were prepared using a standard precipitation method. The Bi2 O3 particles induced apoptosis in human A375 melanoma cells but not human HaCaT keratinocytes or CCD-1090Sk fibroblast cells. This selective apoptosis appears to be associated with a combination of factors: increased particle internalization (2.29 ± 0.41, 1.16 ± 0.08 and 1.66 ± 0.22-fold of control) and enhanced production of reactive oxygen species (ROS) (3.4 ± 0.1, 1.1 ± 0.1 and 2.05 ± 0.17-fold of control) in A375 cells compared to HaCaT and CCD-1090SK cells, respectively. As a high-Z element, bismuth is also an excellent contrast agent for computer tomography, which renders Bi2 O3 a theranostic material. Moreover, Bi2 O3 displays high UV absorption and low photocatalytic activity compared to other semiconducting metal oxides, which opens further potential fields of application as a pigment or as an active ingredient in sunscreens. Overall, this study demonstrates the multifunctional properties of Bi2 O3 particles surrounding the treatment and prevention of melanoma.