NO Oxidation States in Nonheme Iron Nitrosyls: A DMRG-CASSCF Study of {FeNO} Complexes.

Building upon an earlier study of heme-nitrosyl complexes (. , , 20496-20505), we examined a wide range of nonheme {FeNO} complexes (the superscript represents the Enemark-Feltham count) and two dinitrosyl iron complexes using DMRG-CASSCF calculations. Analysis of the wave functions in terms of resonance forms with different [π*(NO)] occupancies (where = 0-4 for mononitrosyl complexes) identified the dominant electronic configurations of {FeNO} and {FeNO} complexes as Fe-NO and Fe-NO, respectively, mirroring our previous findings on heme-nitrosyl complexes.

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.

Transient Kinetic QXAFS Approach for Understanding the RDE-MEA Gap in Fuel Cell (Oxygen Reduction Reaction) Performances of Pt-Based Electrocatalysts.

There is a large gap between the performances indicated by rotating disk electrode (RDE) results in acidic media and the actual performances obtained in membrane-electrode assemblies (MEAs) composed of the same electrocatalysts. It is unclear whether the intrinsic kinetic reactivity of the available surface Pt sites of Pt-based cathode electrocatalysts is similar or different at RDE and in MEA. To address this, we used an operando element-selective time-resolved Pt L-edge quick X-ray absorption fine structure (QXAFS) technique to determine transient response profiles and rate constants, , , and , corresponding to changes in the oxidation states [white line (WL) intensity] and local structures (coordination numbers of Pt-O and Pt-Pt bonds) at Pt sites for nine representative Pt-based cathode electrocatalysts under transient voltage operations, aiming to understand the oxygen reduction reaction (ORR) performance gap between RDE and MEA.

Comparative evaluation of two dose-volume histogram prediction tools for treatment planning: Treatment planning quality and dose verification accuracy.

Purpose: This study aims to compare treatment plans created using RapidPlan and PlanIQ for twelve patients with prostate cancer, focusing on dose uniformity, dose reduction to organs at risk (OARs), plan complexity, and dose verification accuracy. The goal is to identify the tool that demonstrates superior performance in achieving uniform target dose distribution and reducing OAR dose, while ensuring accurate dose verification.

Methods: Dose uniformity in the planning target volume, excluding the rectum, and dose reduction in the OARs (the rectum and bladder) were assessed.

generation of dual-target compounds using artificial intelligence.

Drugs that interact with multiple therapeutic targets are potential high-value products in polypharmacology-based drug discovery, but the rational design remains a formidable challenge. Here, we present artificial intelligence (AI)-based methods to design the chemical structures of compounds that interact with multiple therapeutic target proteins. The molecular structure generation is performed by a fragment-based approach using a genetic algorithm with chemical substructures and a deep learning approach using reinforcement learning with stochastic policy gradients in the framework of generative adversarial networks.

Spatially ordered recruitment of fast muscles in accordance with movement strengths in larval zebrafish.

In vertebrates, skeletal muscle comprises fast and slow fibers. Slow and fast muscle cells in fish are spatially segregated; slow muscle cells are located only in a superficial region, and comprise a small fraction of the total muscle cell mass. Slow muscles support low-speed, low-force movements, while fast muscles are responsible for high-speed, high-force movements.

Switching escape strategies in the parasitic ant cricket Myrmecophilus tetramorii.

Social parasites employ diverse strategies to deceive and infiltrate their hosts in order to benefit from stable resources. Although escape behaviours are considered an important part of these multipronged strategies, little is known about the repertoire of potential escape behaviours and how they facilitate integration into the host colony. Here, we investigated the escape strategies of the parasitic ant cricket Myrmecophilus tetramorii Ichikawa (Orthoptera: Myrmecophilidae) toward its host and non-host ant workers.

PtGd Alloy Nanoparticles from Organometallic Pt and Gd Complexes and Hollow Mesoporous Carbon Spheres: Enhanced Oxygen Reduction Reaction Activity and Durability.

PtGd alloy nanoparticles supported in hollow mesoporous carbon spheres (HMCS; ) were successfully prepared by the thermal reduction of organometallic Pt and Gd complexes without oxygen atoms supported in the pores of HMCS. The structures of PtGd alloy nanoparticles were fully characterized by TEM, HAADF-STEM-EDS, XRD, XAFS, and XPS, suggesting the formation of uniform PtGd alloy nanoparticles with an average particle size of 5.9 nm.

Time-Resolved Probing of the Iodobenzene C-Band Using XUV-Induced Electron Transfer Dynamics.

Time-resolved extreme ultraviolet spectroscopy was used to investigate photodissociation within the iodobenzene C-band. The carbon-iodine bond of iodobenzene was photolyzed at 200 nm, and the ensuing dynamics were probed at 10.3 nm (120 eV) over a 4 ps range.

Phototropin switches between cis- and trans-autophosphorylation in light-induced chloroplast relocation in Marchantia polymorpha.

In the accumulation response, chloroplasts move toward weak blue light (BL) to maximize photosynthetic efficiency; in the avoidance response, they move away from strong BL to reduce photodamage. The BL receptor kinase phototropin (phot) mediates these chloroplast relocation responses, and the chloroplast relocation response requires phot kinase activity. Upon receiving BL, phot undergoes autophosphorylation; however, the molecular mechanisms that regulate chloroplast relocation through phot autophosphorylation remain unclear.

Nanoscale Visualization of Drosophila E-cadherin Ectodomain Fragments and Their Interactions Using DNA Origami Nanoblocks.

The adhesive function of cell surface proteins can be visually assessed through direct observation; however, the underlying structures that mediate adhesion typically remain invisible at the nanoscale level. This hinders knowledge on the diversity of molecular architectures responsible for cell-cell adhesion. Drosophila E-cadherin (DE-cadherin), a classical cadherin with a unique domain structure, demonstrates adhesive function; however, it lacks a structural model that explains its adhesion mechanism.

γ-Secretase Cleaves Bifunctional Fatty Acid-Conjugated Small Molecules with Amide Bonds in Mammalian Cells.

Connecting two small molecules, such as ligands, fluorophores, or lipids, together via a linker with amide bonds is a widely used strategy to generate synthetic bifunctional molecules for various biological and biomedical applications. Such bifunctional molecules have been used in live-cell experiments under the assumption that they should be stable in cells. However, we recently found that a membrane-targeting bifunctional molecule, composed of a lipopeptide and the small-molecule ligand trimethoprim, referred to as mgcTMP, underwent amide-bond cleavage in mammalian cells.

Concise Affinity-Based Purification of Ligated mRNA for Structure-Activity Relationship Studies of Nucleosugar Modification Patterns.

Position-specific nucleoside sugar modifications have been shown to improve the translational activity and stability of chemically synthesized mRNA. For pharmaceutical applications of chemically modified mRNAs, a rapid purification methodology is imperative to identify the optimal modification pattern. However, while the chemical synthesis of mRNAs can be accomplished by splint ligation of oligonucleotide fragments, the current purification method for ligated mRNAs based on denaturing polyacrylamide gel electrophoresis tends to be time consuming.

Deformation Behavior of Microparticle-Based Polymer Films Visualized by AFM Equipped with a Stretching Device.

Understanding the structural changes and property alterations at the nanoscale and microscopic levels is critical to clarifying the deformation behavior and mechanical properties of polymer materials. Especially, in latex films composed of polymer nanoparticles, it is widely accepted that the remaining interfaces between microparticles in the film affect their brittleness. However, detailed information on nanoscale changes of latex films during deformation remains unclear due to technical difficulties in analyzing the microstructures under mechanical stress.

Circularly polarized luminescence induction on a Tb(III) complex with a tris(-butylaryloxide)-functionalized 1,4,7-triazacyclononane ligand coordinating chiral 1-phenylethylamine.

Circularly polarized luminescence (CPL) activity was induced on a racemic Tb complex with a 1,4,7-triazacyclononane-based tris-phenoxide ligand by the coordination of a chiral 1-phenylethylamine ligand to the Tb centre. -Butyl groups at the -position of the phenoxide moieties were found to be important for efficient CPL induction in the Tb complex.

Comprehensive High-Depth Proteomic Analysis of Plasma Extracellular Vesicles Containing Preparations in Rett Syndrome.

Rett syndrome is a neurodevelopmental disorder that affects 1 in 10,000 females. Various treatments have been explored; however, no effective treatments have been reported to date, except for trofinetide, a synthetic analog of glycine-proline-glutamic acid, which was approved by the FDA in 2023. Serological biomarkers that correlate with the disease status of RTT are needed to promote early diagnosis and to develop novel agents.

Single-Molecule Kinetic Observation of Antibody Interactions with Growing Amyloid β Fibrils.

Understanding the dynamic assembly process of amyloid β (Aβ) during fibril formation is essential for developing effective therapeutic strategies against Alzheimer's disease. Here, we employed high-speed atomic force microscopy to observe the growth of Aβ fibrils at the single-molecule level, focusing specifically on their interaction with anti-Aβ antibodies. Our findings show that fibril growth consists of intermittent periods of elongation and pausing, which are dictated by the alternating addition of Aβ monomers to protofilaments.

Nanoscale Structures of Tough Microparticle-Based Films Investigated by Synchrotron X-Ray Scattering and All-Atom Molecular-Dynamics Simulation.

In this study, the nanoscale structures of microparticle-based films are revealed by synchrotron small-angle X-ray scattering (SAXS) and all-atom molecular-dynamics (AA-MD) simulations. The microparticle-based films consisting of the simplest acrylate polymer microparticles are applied as a model because the films are formed without additives and organic solvents and exhibit high toughness properties. The characteristic interfacial thickness () obtained from the SAXS analysis reflects the mixing degree of polymer chains on the microparticle surface in the film.

Development of hydrophobic tag purifying monophosphorylated RNA for chemical synthesis of capped mRNA and enzymatic synthesis of circular mRNA.

We developed phosphorylation reagents with a nitrobenzyl hydrophobic tag and used them for 5'-phosphorylation of chemically or transcriptionally synthesized RNA. The capability of hydrophobic tags to synthesize 5'-monophosphorylated RNA was evaluated based on the yield of the desired oligonucleotides, stability of protecting groups during cleavage/deprotection, separation ability in reverse-phase HPLC (RP-HPLC), and deprotection efficiency after RP-HPLC purification. The results showed that a nitrobenzyl derivative with a tert-butyl group at the benzyl position was most suitable for RNA 5'-phosphorylation.

The Zebrafish Cerebellar Neural Circuits Are Involved in Orienting Behavior.

Deficits in social behavior are found in neurodevelopmental disorders, including autism spectrum disorders (ASDs). Since abnormalities in cerebellar morphology and function are observed in ASD patients, the cerebellum is thought to play a role in social behavior. However, it remains unknown whether the cerebellum is involved in social behavior in other animals and how cerebellar circuits control social behavior.

PdPt/SrTiO:Al-catalysed redox-selective photoreduction of unsaturated carboxylic acids using minimal electron-donor and water.

We developed a semiconductor photocatalyst, Pd-Pt alloy nanoparticle-loaded, Al-doped SrTiO (PdPt/STO:Al), for photoreduction of unsaturated carboxylic acids. Due to the cooperative STO:Al surface and Pd-Pt alloy nanoparticles, the catalyst dispersed in water provided highly redox-selective photoreduction against oxidative degradation of starting materials/products and against reductive evolution of H, where minimal glycolic acid worked as an efficient electron-donating fuel.

Fungal toxin fusicoccin enhances plant growth by upregulating 14-3-3 interaction with plasma membrane H-ATPase.

Fusicoccin-A (FC-A) is a diterpene glucoside produced by a pathogenic fungus. Since its discovery, FC-A has been widely recognized as a phytotoxin that induces stomatal opening and leaf wilting, eventually leading to plant death. In this study, we present the first evidence that FC-A enhances plant growth by stabilizing the protein-protein interaction between plasma membrane (PM) H-ATPase and 14-3-3 in guard cells.

Elastomer Particle Monolayers Formed by the Compression of Poly(methyl acrylate) Microparticles at an Air/Water Interface.

In the previous study (Green Chem., 2023, 25, 3418), highly stretchable and mechanically tough poly(methyl acrylate) (pMA) microparticle-based elastomers can be formed by drying a microparticle-containing aqueous dispersion. This discovery has the potential to overcome the mechanical weakness of industrially produced aqueous latex films.