Reaction of Donor-Acceptor α-Diazo Esters and ,-Dimethylformamide/γ-Lactams To Generate α-Amino-α-aroylethanoates.

Herein, we present a metal-free, concise, and efficient protocol for the intermolecular reaction of amides (lactams) with donor-acceptor α-diazo esters to afford the functionalized α-amino-α-aroylethanoates. -Methyl-2-pyrrolidone (NMP) and ,-dimethylformamide (DMF) are employed as both reagents and solvents, allowing for the incorporation of all units into the products. The reaction is processed by the ester group migration and compatible with a broad range of substrates up to 50 examples.

The Q-Band Energetics and Relaxation of Chlorophylls and as Revealed by Visible-to-Near Infrared Time-Resolved Absorption Spectroscopy.

Chlorophyll (Chl) is the most abundant light-harvesting pigment of oxygenic photosynthetic organisms; however, the Q-band energetics and relaxation dynamics remain unclear. In this work, we have applied femtosecond time-resolved (-TA) absorption spectroscopy in 430-1,700 nm to Chls and in diluted pyridine solutions under selective optical excitation within their Q-bands. The results revealed distinct near-infrared absorption features of the B ← Q and B ← Q transitions in 930-1,700 nm, which together with the steady-state absorption in 400-700 nm unveiled the Q-state energy that lies 1,000 ± 400 and 600 ± 400 cm above the Q-state for Chls and , respectively.

Molecular Clip Strategy of Modified Sulfur Cathodes for High-Performance Potassium Sulfur Batteries.

Potassium-sulfur (K-S) batteries are severely limited by the sluggish reaction kinetics of the cyclooctasulfur (cyclo-S) electrode with low conductivity, which urgently requires a novel cathode to facilitate activity to improve sulfur utilization. In this study, using the wet chemistry method, the molecular clip of Li is created to replace cyclo-S molecular with the highly active chain-like S molecular. The molecular clip strategy effectively lowers the reaction barrier in potassium-sulfur systems, and the stretching of S─S bonds weakens the binding between sulfur atoms, facilitating the transformation of potassium polysulfides (KPSs).

Hydrated cable bacteria exhibit protonic conductivity over long distances.

This study presents the direct measurement of proton transport along filamentous , or cable bacteria. Cable bacteria are filamentous multicellular microorganisms that have garnered much interest due to their ability to serve as electrical conduits, transferring electrons over several millimeters. Our results indicate that cable bacteria can also function as protonic conduits because they contain proton wires that transport protons at distances >100 µm.

Visible-Light-Driven Fluorescence Turn-on Photoswitches With Near Quantitative Photocyclization Yield.

Photoswitchable fluorescent materials have gained significant attention for their potential in advanced information encryption and anti-counterfeiting applications. However, the common use of UV light to trigger the isomerization processes leads to photobleaching and poor fatigue resistance. Visible-light-driven fluorescent photoswitches are highly desirable, but achieving high cyclization yield remains challenging.

Intramolecular Cyclization and Energetic Group Modifications for Thermally Stable and Low-Sensitivity Monocyclic Dinitromethyl Zwitterionic Pyrazoles.

Zwitterionic energetic materials offer a unique combination of high performance and stability, yet their synthesis and stability enhancement remain key challenges. In this study, we report the synthesis of a highly stable (dinitromethyl-functionalized zwitterionic compound, 1-(amino(iminio)methyl)-4,5-dihydro-1H-pyrazol-5-yl)dinitromethanide (), with a thermal decomposition temperature of 215 °C, surpassing that of most previously reported energetic monocyclic zwitterions ( < 150 °C). This compound was synthesized via intramolecular cyclization of a trinitromethyl-functionalized hydrazone precursor.

Spatiotemporal Dynamic Immunomodulation by Infection-Mimicking Gels Enhances Broad and Durable Protective Immunity Against Heterologous Viruses.

Despite their safety and widespread use, conventional protein antigen-based subunit vaccines face significant challenges such as low immunogenicity, insufficient long-term immunity, poor CD8 T-cell activation, and poor adaptation to viral variants. To address these issues, an infection-mimicking gel (IM-Gel) is developed that is designed to emulate the spatiotemporal dynamics of immune stimulation in acute viral infections through in situ supramolecular self-assembly of nanoparticulate-TLR7/8a (NP-TLR7/8a) and an antigen with tannic acid (TA). Through collagen-binding properties of TA, the IM-Gel enables sustained delivery and enhanced retention of NP-TLR7/8a and protein antigen in the lymph node subcapsular sinus of mice for over 7 days, prolonging the exposure of vaccine components in both B cell and T cell zones, leading to robust humoral and cellular responses.

In-Plane Anisotropy in van der Waals NiTeSe Ternary Alloy.

The anisotropic properties of materials profoundly influence their electronic, magnetic, optical, and mechanical behaviors and are critical for a wide range of applications. In this study, the anisotropic characteristics of Ni-based van der Waals materials, specifically NiTe and its alloy NiTeSe, utilizing a combination of comprehensive scanning tunneling microscopy (STM), angle-resolved photoemission spectroscopy (ARPES), and density functional theory (DFT) calculations, are explored. Unlike 1T-NiTe, which exhibits trigonal in-plane symmetry, the substitution of Te with Se in NiTe (resulting in the NiTeSe alloy) induces a pronounced in-plane anisotropy.

Achieving Narrowband and Stable Pure Blue Organic Light-Emitting Diodes by Employing Molecular Vibration Limited Strategies in the Extended π-Conjugated Indolocarbazole Skeleton.

B- and N-heterocyclic fluorophores have reveal promising efficiency in blue organic light-emitting diodes (OLEDs) with small full-width-at-half-maximum (FWHM). However, their structural determinants for spectral broadening and operating stability are still needed to be investigated in further. Herein, a novel multi-N-heterocycles Diindolo[3,2,1jk:3',2',1'jk]dicarbazole[1,2-b:4,5-b] (DIDCz) is proposed to manipulate the emission color toward pure blue region by extending π-conjugation of the N-π-N bridge.

Improving Cognitive Empathy Through Traumatic Brain Injury Experiential Learning: A Novel Mixed Methods Approach for Speech-Language Pathology Graduate Education.

Purpose: The aim of this study was to gauge the impacts of cognitive empathy training experiential learning on traumatic brain injury (TBI) knowledge, awareness, confidence, and empathy in a pilot study of speech-language pathology graduate students.

Method: A descriptive quasi-experimental convergent parallel mixed methods design intervention pilot study (QUAL + QUANT) was conducted with a diverse convenience sample of 19 first- and second-year speech-language pathology graduate students who engaged in a half-day TBI point-of-view simulation. The simulation was co-constructed through a participatory design with those living with TBI based on Kolb's experiential learning model and followed the recommendations for point-of-view simulation ethics.

N-oxide-Functionalized Bipyridines as Strong Electron-Deficient Units to Construct High-Performance n-Type Conjugated Polymers.

Developing low-cost unipolar n-type organic thin-film transistors (OTFTs) is necessary for logic circuits. To achieve this objective, the usage of new electron-deficient building blocks with simple structure and easy synthetic route is desirable. Among all electron-deficient building units, N-oxide-functionalized bipyridines can be prepared through a simple oxidized transformation of bipyridines.

An Albumin-Photosensitizer Supramolecular Assembly with Type I ROS-Induced Multifaceted Tumor Cell Deaths for Photodynamic Immunotherapy.

Photodynamic therapy holds great potentials in cancer treatment, yet its effectiveness in hypoxic solid tumor is limited by the oxygen-dependence and insufficient oxidative potential of conventional type II reactive oxygen species (ROS). Herein, the study reports a supramolecular photosensitizer, BSA@TPE-BT-SCT NPs, through encapsulating aggregation-enhanced emission photosensitizer by bovine serum albumin (BSA) to significantly enhance ROS, particularly less oxygen-dependent type I ROS for photodynamic immunotherapy. The abundant type I ROS generated by BSA@TPE-BT-SCT NPs induce multiple forms of programmed cell death, including apoptosis, pyroptosis, and ferroptosis.

Influence of Photoemission Geometry on Timing and Efficiency in 4D Ultrafast Electron Microscopy.

Broader adoption of 4D ultrafast electron microscopy (UEM) for the study of chemical, materials, and quantum systems is being driven by development of new instruments as well as continuous improvement and characterization of existing technologies. Perhaps owing to the still-high barrier to entry, the full range of capabilities of laser-driven 4D UEM instruments has yet to be established, particularly when operated at extremely low beam currents (~fA). Accordingly, with an eye on beam stability, we have conducted particle tracing simulations of unconventional off-axis photoemission geometries in a UEM equipped with a thermionic-emission gun.

Feasibility and resource utilization of nurse-administered subcutaneous immunoglobulin therapy in antibody deficiency: A cross-sectional study.

Primary and secondary antibody deficiencies (PAD and SAD) are amongst the most prevalent immunodeficiency syndromes, often necessitating long-term immune globulin replacement therapy (IRT). Both intravenous immunoglobulin (IVIG) and subcutaneous immunoglobulin (SCIG) have demonstrated efficacy in antibody deficiency. Comparative analyses of these two routes of administration are limited to nurse-administered IVIG and home therapy with self-administered SCIG.

Preparation, Modification, Quantitation, and Dentin Biomodification Activity of Selectively Enriched Proanthocyanidins.

To date, quantitative analysis of proanthocyanidin (PAC) containing materials including plant extracts and fractions depends on colorimetric assays or phloroglucinolysis/thiolysis combined with UV-HPLC analysis. Such assays are of limited accuracy, particularly lack specificity, require extensive sample preparation and degradation, and need appropriate physical reference standards. To address this analytical challenge and toward our broader goal of developing new plant-sourced biomaterials that chemically and mechanically modulate the properties of dental tissue for clinical interventions, we have characterized 12 different PAC DESIGNER (Depletion and Enrichment of Select Ingredients Generating Normalized Extract Resources) materials.

Two-Dimensional Phototransistors with van der Waals Superstructure Contacts for High-Performance Photosensing.

Semiconducting transition metal dichalcogenides (TMDs) possess exceptional photoelectronic properties, rendering them excellent channel materials for phototransistors and holding great promise for future optoelectronics. However, the attainment of high-performance photodetection has been impeded by challenges pertaining to electrical contact. To surmount this obstacle, we introduce a phototransistor architecture, in which the WS channel is connected with an alternating WS-WSe strip superstructure, strategically positioned alongside the source and drain contact regions.

Hydrogen-Rich Saline Combined With Vacuum Sealing Drainage Promotes Wound Healing by Altering Biotin Metabolism.

Impaired wound healing affects the life quality of patients and causes a substantial financial burden. Hydrogen-rich medium is reported to have antioxidant and anti-inflammatory effects. However, the role of hydrogen-rich saline (HRS) in cutaneous wound healing remains largely unexplored, especially by metabolomics.

Employing Triphenylene-Based, Layered, Conductive Metal-Organic Framework Materials as Electrochemical Sensors for Nitric Oxide in Aqueous Media.

This paper describes the first use of conductive metal-organic frameworks as the active material in the electrochemical detection of nitric oxide in aqueous solution. Four hexahydroxytriphenylene (HHTP)-based MOFs linked with first-row transition metal nodes (M = Co, Ni, Cu, Zn) were compared as thin-film working electrodes for promoting oxidation of NO using voltammetric and amperometric techniques. Cu- and Ni-linked MOF analogs provided signal enhancement of 5- to 7-fold over a control glassy carbon electrode (SA = 6.

Novel Foamed Magnesium Phosphate Antimicrobial Bone Cement for Bone Augmentation.

In dental implant surgery, infection is identified as the primary factor contributing to the failure of bone grafts. There is an urgent need to develop bone graft materials possessing antibacterial characteristics to facilitate bone regeneration. Magnesium phosphate bone cement (MPC) is highly desirable for bone regeneration due to its favorable biocompatibility, plasticity, and osteogenic capabilities.

Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization.

Planar chirality found tremendous use in many fields, such as chemistry, optics, and materials science. In particular, planar chiral [2.2]paracyclophanes (PCPs) are a type of structurally interesting and practically useful chiral compounds bearing unique electronic and photophysical properties and thus have been widely used in π-stacking polymers, organic luminescent materials, and as a valuable toolbox for developing chiral ligands or organocatalysts.

In Situ Self-Assembled Naringin/ZIF-8 Nanoparticle-Embedded Bacterial Cellulose Sponges for Infected Diabetic Wound Healing.

The treatment of diabetic foot ulcers (DFUs) represents a significant challenge due to the complexity of the wound microenvironment. Several factors, including infection, inflammation, and impaired angiogenesis, can complicate the healing process and reduce the effectiveness of current clinical treatments. To address these challenges, this work develops a multifunctional sponge containing a zeolitic imidazolate framework-8/bacterial cellulose (ZIF-8/BC) matrix loaded with the antioxidant naringin (Nar).

Modulating Perovskite Surface Energetics Through Tuneable Ferrocene Interlayers for High-Performance Perovskite Solar Cells.

Achieving rational control over chemical and energetic properties at the perovskite/electron transport layer (ETL) interface is crucial for realizing highly efficient and stable next-generation inverted perovskite solar cells (PSCs). To address this, we developed multifunctional ferrocene (Fc)-based interlayers engineered to exhibit adjustable passivating and electrochemical characteristics. These interlayers are designed to minimize non-radiative recombination and, to modulate the work function (WF) and uniformity of the perovskite surface, thereby enhancing device performance.

Manipulation of Surface Spin Configurations for Enhanced Performance in Oxygen Evolution Reactions.

studies of the relationship between surface spin configurations and spin-related electrocatalytic reactions are crucial for understanding how magnetic catalysts enhance oxygen evolution reaction (OER) performance under magnetic fields. In this work, 2D FeSe nanosheets with rich surface spin configurations are synthesized via chemical vapor deposition. magnetic force microscopy and Raman spectroscopy reveal that a 200 mT magnetic field eliminates spin-disordered domain walls, forming a spin-ordered single-domain structure, which lowers the OER energy barrier, as confirmed by theoretical calculations.

Enhanced bone cement for fixation of prosthetic joint utilizing nanoparticles.

Bone cement is commonly utilized to secure prosthetic joints in the body because of its robust fixation, stability, biocompatibility, and immediate load-bearing capability. However, issues such as loosening, leakage, and insufficient bioactivity can lead to its failure. Therefore, improving its mechanical, physical, and biological properties is crucial for enhancing its efficiency.

Low-cost male urogenital simulator for penile implant surgery training: a 3D printing approach.

Background: Penile implant surgery is the standard surgical treatment for end-stage erectile dysfunction. However, the growing complexity of modern high-tech penile prostheses has increased the demand for more practical training opportunities. The most advanced contemporary training methods involve simulation training using cadavers, with costs exceeding $5,000 per cadaver, inclusive of biohazard fees.