Squaric Acid-Containing Hole-Collecting Monolayer Materials for p-i-n Perovskite Solar Cells.

The development of hole-collecting materials is indispensable to improving the performance of perovskite solar cells (PSCs). To date, several anchorable molecules have been reported as effective hole-collecting monolayer (HCM) materials for p-i-n PSCs. However, their structures are limited to well-known electron-donating skeletons, such as carbazole, triarylamine, etc.

An Icosahedral 55-Atom Iron Hydride Cluster Protected by Tri--butylphosphines.

Nanoclusters are nanometer-sized molecular compounds characterized by significant metal-metal bonding and low average oxidation states, and they exhibit unique properties distinct from those of small metal complexes or nanoparticles. Unlike noble metals stable in metallic forms, the synthesis of nanometer-sized iron clusters has been precluded by the relatively weak iron-iron bonds and the high reactivity of low oxidation state iron, despite the extensive history of molecular iron compounds. Here, we report the synthesis and characterization of a cationic 55-atom iron cluster with a 1.

Organic photoredox-catalyzed unimolecular PCET of benzylic alcohols.

Proton-coupled electron transfer (PCET) is a crucial chemical process involving the simultaneous or sequential transfer of protons and electrons, playing a vital role in biological processes and energy conversion technologies. This study investigates the use of an organic photoredox catalyst to facilitate a unimolecular PCET process for the generation of alkyl radicals from benzylic alcohols, with a particular focus on alcohols containing electron-rich arene units. By employing a benzophenone derivative as the catalyst, the reaction proceeds efficiently under photoirradiation, achieving significant yields without the need for a Brønsted base.

Thiazolidinone-Based Electron-Collecting Monolayers for n-i-p Perovskite Solar Cells.

The development of efficient electron-collecting monolayer materials is desired to lower manufacturing costs and improve the performance of regular (negative-intrinsic-positive, n-i-p) type perovskite solar cells (PSCs). Here, we designed and synthesized four electron-collecting monolayer materials based on thiazolidinone skeletons, with different lowest-unoccupied molecular orbital (LUMO) levels (rhodanine or thiazolidinedione) and different anchoring groups to the transparent electrode (phosphonic acid or carboxylic acid). These molecules, when adsorbed on indium tin oxide (ITO) substrates, lower the work function of ITO, decreasing the energy barrier for electron extraction at the ITO/perovskite interface and improving the device performance.

Photoredox-Catalyzed Site-Selective Intermolecular C(sp)-H Alkylation of Tetrahydrofurfuryl Alcohol Derivatives.

4'-Selective alkylation of nucleosides has been recognized as one of the ideal and straightforward approaches to chemically modified nucleosides, but such a transformation has been scarce and less explored. In this Letter, we combine a visible-light-mediated photoredox catalysis and hydrogen atom transfer (HAT) auxiliary to achieve β-C(sp)-H alkylation of alcohol on tetrahydrofurfuryl alcohol scaffolds and exploit it for 4'-selective alkylation of nucleosides. The reaction involves an intramolecular 1,5-HAT process and stereocontrolled Giese addition of the resultant radicals.

Covalent Plant Natural Product that Potentiates Antitumor Immunity.

Despite the unprecedented therapeutic potential of immune checkpoint antibody therapies, their efficacy is limited partly by the dysfunction of T cells within the cancer microenvironment. Combination therapies with small molecules have also been explored, but their clinical implementation has been met with significant challenges. To search for antitumor immunity activators, the present study developed a cell-based system that emulates cancer-attenuated T cells.

Molecular Design of Hole-Collecting Materials for Co-Deposition Processed Perovskite Solar Cells: A Tripodal Triazatruxene Derivative with Carboxylic Acid Groups.

High-performance and cost-effective hole-collecting materials (HCMs) are indispensable for commercially viable perovskite solar cells (PSCs). Here, we report an anchorable HCM composed of a triazatruxene core connected with three alkyl carboxylic acid groups (). In contrast to the phosphonic acid-containing tripodal analog (), molecules can form a hydrophilic monolayer on a transparent conducting oxide surface, which is beneficial for subsequent perovskite film deposition in the traditional layer-by-layer fabrication process.

Multiple Near-Infrared Chromisms of a Heteromerous Overcrowded Ethylene with Large Permanent Dipole Moment.

An overcrowded ethylene composed of electron-donating anion, naphthoxide, and electron-accepting cation, acridinium, has been synthesized. It is in equilibrium between a folded conformer having a smaller permanent dipole moment with visible light absorption and a twisted conformer having a larger permanent dipole moment with NIR light absorption. The overcrowded ethylene shows multiple NIR chromisms, such as solvatochromism, thermochromism, mechanochromism, vapochromism, halochromism, and amphoteric electrochromisms, which are caused by the conformational change between folded and twisted conformers or by controlling the energy difference between the HOMO of the donor moiety and the LUMO of the acceptor moiety.

Doubly Linked Azulene Dimer: A Novel Non-benzenoid Isomer of Perylene.

We report herein the synthesis of an unprecedented isomer of perylene, dicyclohepta[cd,fg]-as-indacene bearing two phenyl groups (1-Ph) by the nickel-mediated intramolecular homocoupling of a 4,4'-biazulene derivative (2). The X-ray crystallographic analysis and theoretical calculations revealed that 1-Ph adopts a unique helically twisted geometry although the local aromaticity of azulene moieties was preserved. The double covalent linkage of the two azulene skeletons imparts significant orbital interaction, which affords near-infrared (NIR) absorption (up to 1720 nm) and remarkable redox behaviors despite its closed-shell electronic structure.

Orderly Arranged Cubic Quantum Dots along Supramolecular Templates of Naphthalenediimide Aggregates.

Precise control of assembled structures of quantum dots (QDs) is crucial for realizing the desired photophysical properties, but this remains challenging. Especially, the one-dimensional (1D) control is rare due to the nearly isotropic nature of QDs. Herein, we propose a novel strategy for controlling the 1D-arrangement range of cubic perovskite QDs in solution based on the morphological modification of a supramolecular polymer (SP) template.

Single-isomer bis(pyrrolidino)fullerenes as electron-transporting materials for tin halide perovskite solar cells.

Although fullerene bisadducts are promising electron-transporting materials for tin halide perovskite solar cells, they are generally synthesized as a mixture of isomeric products that require a complicated separation process. Here, we introduce a phenylene-bridged bis(pyrrolidino)fullerene, Bis-PC, which forms only a single isomer due to geometrical restriction. When used in a tin perovskite solar cell with a PEAFASnI (PEA: phenylethylammonium and FA: formamidinium) light absorption layer, the resulting open-circuit voltage ( ) was 0.

Inter- and Intrasublattice Spin Mixing Conductance of the Antiferromagnetic Spin Pumping Effect in α-Fe_{2}O_{3}/Pt.

The spin pumping effect in antiferromagnets, which ultimately converts THz waves into a spin current, is the key physical mechanism leading to an essential function which harnesses the THz technology and spintronics. Here, we report thorough experimental investigations of the spin current induced by the antiferromagnetic spin pumping effect in epitaxial α-Fe_{2}O_{3} thin films having two distinct dynamic modes and unambiguously show that both the inter- and intrasublattice spin mixing conductance are equally substantial. Our experimental insight is an important advance for understanding the physics of transduction between the spin current and the staggered magnetization dynamics at THz frequency.

KCNN4 as a genomic determinant of cytosolic delivery by the attenuated cationic lytic peptide L17E.

The development of a cytosolic delivery strategy for biopharmaceuticals is one of the central issues in drug development. Knowledge of the mechanisms underlying these processes may also pave the way for the discovery of novel delivery systems. L17E is an attenuated cationic amphiphilic lytic (ACAL) peptide developed by our research group that shows promise for cytosolic antibody delivery.

Performance and stability analysis of all-perovskite tandem photovoltaics in light-driven electrochemical water splitting.

All-perovskite tandem photovoltaics are a potentially cost-effective technology to power chemical fuel production, such as green hydrogen. However, their application is limited by deficits in open-circuit voltage and, more challengingly, poor operational stability of the photovoltaic cell. Here we report a laboratory-scale solar-assisted water-splitting system using an electrochemical flow cell and an all-perovskite tandem solar cell.

Stabilization of oxygen vacancy ordering and electrochemical-proton-insertion-and-extraction-induced large resistance modulation in strontium iron cobalt oxides Sr(Fe,Co)O.

Electrochemically inserting and extracting hydrogen into and from solids are promising ways to explore materials' phases and properties. However, it is still challenging to identify the structural factors that promote hydrogen insertion and extraction and to develop materials whose functional properties can be largely modulated by inserting and extracting hydrogen through solid-state reactions at room temperature. In this study, guided by theoretical calculations on the energies of oxygen reduction and hydrogen insertion reactions with oxygen-deficient perovskite oxides, we demonstrated that the oxygen vacancy ordering in Sr(FeCo)O (SFCO) epitaxial films can be stabilized by increasing the Co content (x ≥ 0.

Steering perovskite precursor solutions for multijunction photovoltaics.

Multijunction photovoltaics (PVs) are gaining prominence owing to their superior capability of achieving power conversion efficiencies (PCEs) beyond the radiative limit of single-junction cells, where improving narrow bandgap tin-lead perovskites is critical for thin-film devices. With a focus on understanding the chemistry of tin-lead perovskite precursor solutions, we herein find that Sn(II) species dominate interactions with precursors and additives and uncover the exclusive role of carboxylic acid in regulating solution colloidal properties and film crystallisation, and ammonium in improving film optoelectronic properties. Materials that combine these two function groups, amino acid salts, considerably improve the semiconducting quality and homogeneity of perovskite films, surpassing the effect of the individual functional groups when introduced as part of separate molecules.

Genome-resolved year-round dynamics reveal a broad range of giant virus microdiversity.

Giant viruses are crucial for marine ecosystem dynamics because they regulate microeukaryotic community structure, accelerate carbon and nutrient cycles, and drive the evolution of their hosts through co-evolutionary processes. Previously reported long-term observations revealed that these viruses display seasonal fluctuations in abundance. However, the underlying genetic mechanisms driving such dynamics of these viruses remain largely unknown.

Dithienoarsinines: stable and planar π-extended arsabenzenes.

Stable planar dithienoarsinines were synthesized and structurally characterized. These compounds exhibit monomeric structures in the solution and solid states, avoiding dimerization, even in the absence of steric protection. They exhibited high global aromaticity with 14 or 22π-electron systems.

Unveiling the Antithermal Quenching Behavior in 0D Inorganic Metal Halide CsInCl(HO) Mediated by Upconversion Emission.

Inorganic metal halides (IMHs) often suffer from severe fluorescence thermal quenching, limiting their application at elevated temperatures. Therefore, the exploration of IMHs exhibiting antithermal quenching (ATQ) behavior is of great importance. In this study, we developed a green synthetic route using a solvent evaporation method to successfully synthesize the 0D IMHs CsInCl(HO).

Revealing the Dynamic Aspects of Photoinduced Halide Segregation in Mixed-Halide CsFAPbIBr Perovskite Films Using a Hyperspectral Imaging Technique.

The band gap energy of halide perovskite semiconductors is manipulated by controlling the halide composition, and mixed halide perovskites are receiving much attention as top cell materials for tandem solar cells. To understand dynamic aspects of photoinduced halide segregation in mixed-halide perovskite films, we use a hyperspectral imaging technique. We reveal the space- and time-resolved photoluminescence (PL) spectra of CsFAPbIBr perovskite films during prolonged light illumination.

Single-Sided Delocalized Polarization of the C Cage and Reduced Infrared Intensities and Dipole Moment of HO@C.

The C fullerene cage can encapsulate a small molecule like water and provides room to leave the encapsulated component rather isolated, but the true nature of the intracomplex interactions should be further elucidated for better understanding and utility of this series of complexes. Here, an analysis toward this goal is conducted for HO@C by infrared spectral measurements and theoretical calculations. It is shown that the response of the π electrons of the C cage upon encapsulating a water molecule is single-sided and delocalized in that the electron density is partially transferred from the - side to the + side of the cage (when the axis is taken along the water dipole) but almost only inside the cage, explaining the significant reduction of the dipole moment and the infrared intensities.

Modulatory effects of CNNM4 on protein- l -isoaspartyl- O -methyltransferase repair function during alcohol-induced hepatic damage.

Background And Aims: Alcohol-associated liver disease (ALD) is a leading cause of liver-related mortality worldwide, with limited treatment options beyond abstinence and liver transplantation. Chronic alcohol consumption has been linked to magnesium (Mg 2+ ) deficiency, which can influence liver disease progression. The mechanisms underlying Mg 2+ homeostasis dysregulation in ALD remain elusive.