Understanding Oxygen-Induced Reactions and Their Impact on n-Type Polymeric Mixed Conductor-Based Devices.

Electron transporting (n-type) polymeric mixed conductors are an exciting class of materials for devices with aqueous electrolyte interfaces, such as bioelectronic sensors, actuators, and soft charge storage systems. However, their charge transport performance falls short of their p-type counterparts, primarily due to electrochemical side reactions such as the oxygen reduction reaction (ORR). To mitigate ORR, a common strategy in n-type organic semiconductor design focuses on lowering the lowest unoccupied molecular orbital (LUMO) level.

Sensing Hachimoji DNA Bases with Janus MoSH Monolayer Nanodevice: Insights from Density Functional Theory (DFT) and Non-Equilibrium Green's Function Analysis.

Detection of nucleobases is of great significance in DNA sequencing, which is one of the main goals of the Human Genome Project. The synthesis of Hachimoji DNA, an artificial genetic system with eight nucleotide bases, has induced a transformative shift in genetic research and biosensing. Here, we present a systematic investigation of the adsorption behavior and electronic transport properties of natural and modified DNA bases on a Janus molybdenum sulfur hydride (MoSH) monolayer using density functional theory (DFT) and nonequilibrium Green's function (NEGF) methods.

Integrating Interactive Ir Atoms into Titanium Oxide Lattice for Proton Exchange Membrane Electrolysis.

Iridium (Ir)-based oxide is the state-of-the-art electrocatalyst for acidic water oxidation, yet it is restricted to a few Ir-O octahedral packing modes with limited structural flexibility. Herein, the geometric structure diversification of Ir is achieved by integrating spatially correlated Ir atoms into the surface lattice of TiO and its booting effect on oxygen evolution reaction (OER) is investigated. Notably, the resultant i-Ir/TiO catalyst exhibits much higher electrocatalytic activity, with an overpotential of 240 mV at 10 mA cm and excellent stability of 315 h at 100 mA cm in acidic electrolyte.

Reductive coupling of allenyl/allyl carbonate with alkyne under dual cobalt-photoredox catalysis.

Skipped dienes are among the most prevalent motifs in a vast array of natural products, medicinal compounds, and fatty acids. Herein, we disclose a straightforward one-step reductive protocol under Co/PC for the synthesis of diverse 1,4-dienes with excellent regio- and stereoselectivity. The protocol employs allenyl or allyl carbonate as π-allyl source, allowing for the direct synthesis of skipped diene with a broad range of alkynes including terminal alkynes, propargylic alcohols, and internal alkynes.

Local compressive strain-induced anti-corrosion over isolated Ru-decorated CoO for efficient acidic oxygen evolution.

Enhancing corrosion resistance is essential for developing efficient electrocatalysts for acidic oxygen evolution reaction (OER). Herein, we report the strategic manipulation of the local compressive strain to reinforce the anti-corrosion properties of the non-precious CoO support. The incorporation of Ru single atoms, larger in atomic size than Co, into the CoO lattice (Ru-CoO), triggers localized strain compression and lattice distortion on the Co-O lattice.

Interfacial Engineering of MoS via Boron-Doping for Electrochemical N-to-NH Conversion.

The electrocatalytic synthesis of ammonia (NH) through the nitrogen reduction reaction (NRR) under ambient temperature and pressure is emerging as an alternative approach to the conventional Haber-Bosch process. However, it remains a significant challenge due to poor kinetics, low nitrogen (N) solubility in aqueous electrolytes, and the competing hydrogen evolution reaction (HER), which can significantly impact NH production rates and Faradaic efficiency (FE). Herein, a rationally designed boron-doped molybdenum sulfide (B-Mo-MoS) electrocatalyst is reported that effectively enhances N reduction to  NH with an onset potential of -0.

The Paradoxical Influence of Hydrothermally Treated Zeolites on the Hydrocarbon Pool Mechanism.

Understanding the mechanistic intricacies of hydrothermally treated zeolite is crucial for valorizing any oxygen-containing renewable feedstocks (e. g., methanol, carbon dioxide, biomass).

A Comprehensive Multireference Study of Excited-State Ni-Br Bond Homolysis in (dtbbpy)Ni(aryl)(Br).

The mechanism of visible light-driven Ni-C(aryl) bond homolysis in (2,2'-bipyridine)Ni(aryl)(halide) complexes, which play a crucial role in metallaphotoredox catalysis for cross-coupling reactions, has been well studied. Differently, the theoretical understanding of Ni-halide bond homolysis remains limited. In this study, we introduce a novel electronic structural framework to elucidate the mechanisms underlying photoinduced Ni-Br bond rupture in the (dtbbpy)Ni(aryl)(Br) complex.

Outcome Measures of Open versus Minimally Invasive Surgery for Thoracolumbar Spinal Traumatic Fractures: A Systematic Review and Meta-Analysis.

To evaluate the efficacy of open and percutaneous pedicle screw fixation in the treatment of thoracolumbar fractures. Online databases MEDLINE (PubMed), SCOPUS, and Cochrane were searched for English language articles published between January 2001 and December 2023, limited to articles that included the clinical and radiological outcomes of adult patients. The main outcome measures of the study were the Oswestry Disability Index (ODI), the Numeric Rating Scale (NRS) score, and the Cobb angle.

Fluorescence guidance in skull base surgery: Applications and limitations - A systematic review.

Introduction: Intraoperative fluorescence guidance is a well-established surgical adjunct in high-grade glioma surgery. In contrast, the clinical use of such dyes and technology has been scarcely reported in skull base surgery.

Research Question: We aimed to systematically review the clinical applications of different fluorophores in both open and endonasal skull base surgery.

Modulating Decarboxylative Oxidation Photocatalysis by Ligand Engineering of Atomically Precise Copper Nanoclusters.

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu(Nap)(PPh)H (hereafter CuNap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions.

Endonasal Route for Tuberculum and Planum Meningiomas.

Tuberculum and planum meningiomas are challenging tumors per their critical location and neurovascular relationships. The standard treatment is usually represented by complete tumor removal, being the transcranial approaches the well-established routes. During the last decades, novel surgical routes have been experimented with emphasis on the concept of minimal invasive approaches.

High-Throughput Computational Screening of Metal Sulfides for the Chemical Looping Elemental Decomposition of HS.

Hydrogen sulfide is a significant byproduct of oil and gas production and is typically recovered as elemental sulfur, a low-value commodity. In recent years, there have been efforts to upgrade HS through elemental decomposition to S and H, an essential energy carrier in a sustainable economy. Among the promising approaches is thermocatalytic looping, which involves a sulfide-based redox pair.

Halogen Bonding Initiated Difunctionalization of [1.1.1]Propellane via Photoinduced Polarity Match Additions.

Bicyclo[1.1.1]pentane (BCP), recognized as a bioisostere for para-disubstituted benzene, has gained widespread interest in drug development due to its ability to enhance the physicochemical properties of pharmaceuticals.

Electrocatalytic Hydrogen Generation by Ni-PNP Pincer Complexes: Role of Phosphorus Substituents in Tuning the Reactivity.

Electrocatalytic hydrogen evolution reaction (eHER) is crucial in addressing the growing global energy demand. Although nickel-pincer-based molecular complexes, varying in donor atoms, were studied previously for eHER, the impact of variations in the substituents attached to the donor atoms was not investigated. Herein, three air-stable PNP-based Ni-pincer complexes [R1=R2=Ph (7); R1=R2=Bu (9); R1=Bu, R2=Ph (10)], varying solely in P-substituents, were studied in acetonitrile.

Highly Dispersed Pd@ZIF-8 for Photo-Assisted Cross-Couplings and CO to Methanol: Activity and Selectivity Insights.

Our study unveils a pioneering methodology that effectively distributes Pd species within a zeolitic imidazolate framework-8 (ZIF-8). We demonstrate that Pd can be encapsulated within ZIF-8 as atomically dispersed Pd species that function as an excited-state transition metal catalyst for promoting carbon-carbon (C-C) cross-couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250 °C, forming Pd metal nanoparticles encapsulated in ZIF-8.

KLHL14 and E-Cadherin Nuclear Co-Expression as Predicting Factor of Nonfunctioning PitNET Invasiveness: Preliminary Study.

Novel diagnostic and therapeutic approaches are needed to improve the clinical management of nonfunctioning pituitary neuroendocrine tumors (NF-PitNETs). Here, the expression of two proteins controlling the epithelial-mesenchymal transition (EMT)-an underlying NF-PitNET pathogenic mechanism-were analyzed as prognostic markers: E-cadherin (E-Cad) and KLHL14. The immunohistochemistry characterization of KLHL14 and E-Cad subcellular expression in surgical specimens of 12 NF-PitNET patients, with low and high invasiveness grades (respectively, Ki67 < and ≥3%) was carried out.

Thermodynamic and Kinetic Behaviors of Electrolytes Mediated by Intermolecular Interactions Enabling High-Performance Lithium-Ion Batteries.

Electrolyte solvation chemistry regulated by lithium salts, solvents, and additives has garnered significant attention since it is the most effective strategy for designing high-performance electrolytes in lithium-ion batteries (LIBs). However, achieving a delicate balance is a persistent challenge, given that excessively strong or weak Li-solvent coordination markedly undermines electrolyte properties, including thermodynamic redox stability and Li-desolvation kinetics, limiting the practical applications. Herein, we elucidate the crucial influence of solvent-solvent interactions in modulating the Li-solvation structure to enhance electrolyte thermodynamic and kinetic properties.

Selectivity descriptors of the catalytic -hexane cracking process over 10-membered ring zeolites.

Zeolite-mediated catalytic cracking of alkanes is pivotal in the petrochemical and refining industry, breaking down heavier hydrocarbon feedstocks into fuels and chemicals. Its relevance also extends to emerging technologies such as biomass and plastic valorization. Zeolite catalysts, with shape selectivity and selective adsorption capabilities, enhance efficiency and sustainability due to their well-defined network of pores, dimensionality, cages/cavities, and channels.

From data to practice: brain meningioma treatment in elderly patients - a survey of the Italian Society of Neurosurgery (SINch®) and systematic review and meta-analysis.

The management of meningioma in elderly patients (MEP) presents a complex and evolving challenge. Data available offer conflicting information on treatment options and complications. This survey aimed to examine the current approach to MEP, comparing the national profile to data in the current literature.

Transorbital Route to Intracranial Space.

The endoscopic superior eyelid transorbital approach has emerged as a notable and increasingly utilized surgical technique in recent years. This chapter presents an overview of the approach, tracing its historical development and highlighting its growing acceptance within the skull base community.Beginning with an introduction and historical perspective, the chapter outlines the evolution of the transorbital approach, shedding light on its origins and the factors driving its adoption.

Temozolomide based treatment in glioblastoma: 6 vs. 12 months.

The Stupp regimen remains the standard treatment for newly diagnosed glioblastomas, although the prognosis remains poor. Several temozolomide alternative schedules have been studied, with extended adjuvant treatment (>6 cycles of temozolomide) frequently used, although different trials have indicated contrasting results. Survival data of 87 patients who received 6 ('6C' group) or 12 ('12C' group) cycles of temozolomide were collected between 2012 and 2022.

Low-Temperature and Fast-Charging Lithium Metal Batteries Enabled by Solvent-Solvent Interaction Mediated Electrolyte.

Lithium metal batteries utilizing lithium metal as the anode can achieve a greater energy density. However, it remains challenging to improve low-temperature performance and fast-charging features. Herein, we introduce an electrolyte solvation chemistry strategy to regulate the properties of ethylene carbonate (EC)-based electrolytes through intermolecular interactions, utilizing weakly solvated fluoroethylene carbonate (FEC) to replace EC, and incorporating the low-melting-point solvent 1,2-difluorobenzene (2FB) as a diluent.

Unveiling structural and energetic characterization of the emissive RNA alphabet anchored in the methylthieno[3,4-]pyrimidine heterocycle core.

This study presents a comprehensive theoretical exploration of the fluorescent non-natural emissive nucleobases- A, G, C, and U derived from the methylthieno[3,4-]pyrimidine heterocycle. Our calculations, aligning with experimental findings, reveal that these non-natural bases exert minimal influence on the geometry of classical Watson-Crick base pairs within an RNA duplex, maintaining H-bonding akin to natural bases. In terms of energy, the impact of the modified bases, but for G, is also found to be little significant.