Amphoteric reactivity of iron(III)-hydroperoxo complex generated from proton- and salicylate-assisted dioxygen activation.

We report the synthesis and characterization of an iron(III)-hydroperoxo complex generated from salicylate-assisted dioxygen activation by a cation-liganded iron(II) complex. Spectroscopic and theoretical data revealed stabilization of the end-on hydroperoxo ligand, and mechanistic insights, including a "V-shaped" Hammett plot, were confirmed by conducting oxygen atom transfer and proton-coupled electron transfer reactions.

Reduction-Assisted Calcination Enhances the Photocatalytic Activity of ZnO and WO Nanoparticles in Biomass Conversion.

Rising energy needs and environmental issues have prompted the creation of effective and affordable photocatalysts for converting biomass. Utilizing abundant biomass, oxidation of 5-hydroxymethylfurfural (HMF) emerges as a method for generating high-value chemicals from biomass, offering an alternative to fossil fuels. We synthesized defect-engineered metal oxides (ZnO and WO) by calcination with NaBH as a reducing agent.

Targeting isoforms of RON kinase (MST1R) drives antitumor efficacy.

Recepteur d'origine nantais (RON, MST1R) is a single-span transmembrane receptor tyrosine kinase (RTK) aberrantly expressed in numerous cancers, including various solid tumors. How naturally occurring splicing isoforms of RON, especially those which are constitutively activated, affect tumorigenesis and therapeutic response, is largely unknown. Here, we identified that presence of activated RON could be a possible factor for the development of resistance against anti-EGFR (cetuximab) therapy in colorectal cancer patient tissues.

Optical Coherence Tomographic Optic Nerve Head Morphology in Myopia III: The Exposed Neural Canal Region in Healthy Eyes-Implications for High Myopia.

Purpose: To determine the prevalence and magnitude of optical coherence tomography (OCT) exposed neural canal (ENC), externally oblique choroidal border tissue (EOCBT), and exposed scleral flange (ESF) regions in 362 non-highly myopic (spherical equivalent -6.00 to 5.75 diopters) eyes of 362 healthy subjects.

Mutant PIK3CA as a negative predictive biomarker for treatment with a highly selective PIM1 inhibitor in human colon cancer.

Significant improvement in targeted therapy for colorectal cancer (CRC) has occurred over the past few decades since the approval of the EGFR inhibitor cetuximab. However, cetuximab is used only for patients possessing the wild-type oncogene KRAS, NRAS, and BRAF, and even most of these eventually acquire therapeutic resistance, via activation of parallel oncogenic pathways such as RAS-MAPK or PI3K/Akt/mTOR. The two aforementioned pathways also contribute to the development of therapeutic resistance in CRC patients, due to compensatory and feedback mechanisms.

Hint from an Enzymatic Reaction: Superoxide Dismutase Models Efficiently Suppress Colorectal Cancer Cell Proliferation.

Superoxide dismutases (SODs) are essential antioxidant enzymes that prevent massive superoxide radical production and thus protect cells from damage induced by free radicals. However, this concept has rarely been applied to directly impede the function of driver oncogenes, thus far. Here, leveraging efforts from SOD model complexes, we report the novel finding of biomimetic copper complexes that efficiently scavenge intracellularly generated free radicals and, thereby, directly access the core consequence of colorectal cancer suppression.

Polypropylene microplastics promote metastatic features in human breast cancer.

Microplastics (MPs) are now a global issue due to increased plastic production and use. Recently, various studies have been performed in response to the human health risk assessment. However, these studies have focused on spherical MPs, which have smooth edges and a spherical shape and account for less than 1% of MPs in nature.

Association of overexpressed carboxyl-terminal amyloid precursor protein in brains with altered glucose metabolism and liver toxicity.

Alzheimer's disease (AD) is the most prevalent neurodegenerative disease. The deposition of amyloid plaques mainly composed of amyloid beta (Aβ) is observed in brain regions in AD patients. AD presents with similar pathophysiology to that of metabolic syndrome, including glucose and insulin resistance.

OCT Optic Nerve Head Morphology in Myopia II: Peri-Neural Canal Scleral Bowing and Choroidal Thickness in High Myopia-An American Ophthalmological Society Thesis.

Purpose: To use optical coherence tomography (OCT) to characterize optic nerve head (ONH) peri-neural canal (pNC) scleral bowing (pNC-SB) and pNC choroidal thickness (pNC-CT) in 69 highly myopic and 138 healthy, age-matched, control eyes.

Design: Cross-sectional, case control study.

Methods: Within ONH radial B-scans, Bruch membrane (BM), BM opening (BMO), anterior scleral canal opening (ASCO), and pNC scleral surface were segmented.

Agile and versatile climbing on ferromagnetic surfaces with a quadrupedal robot.

A climbing robot that can rapidly move on diverse surfaces such as floors, walls, and ceilings will have an enlarged operational workspace compared with other terrestrial robots. However, the climbing skill of robots in such environments has been limited to low speeds or simple locomotion tasks. Here, we present an untethered quadrupedal climbing robot called MARVEL (magnetically adhesive robot for versatile and expeditious locomotion), capable of agile and versatile climbing locomotion in ferromagnetic environments.

Designed Amyloid Fibers with Emergent Melanosomal Functions.

Short peptides designed to self-associate into amyloid fibers with metal ion-binding ability have been used to catalyze various types of chemical reactions. This manuscript demonstrates that one of these short-peptide fibers coordinated with Cu can exhibit melanosomal functions. The coordinated Cu and the amyloid structure itself are differentially functional in accelerating oxidative self-association of dopamine into melanin-like species and in regulating their material properties (e.

Catalytic approach to metabolism of atractylenolide III using biomimetic iron-porphyrin complexes.

Atractylenolide III (AT-III) is a pharmacologically effective phytochemical and is known to be oxygenated during systemic metabolism mainly by cytochrome P450 enzymes (CYP450s), iron-containing porphyrin-based oxygenases. In rat plasma samples, the oxygenated metabolite of orally ingested AT-III was determined using liquid chromatography/mass spectrometry and the oxygenated form of AT-III was maintained at higher levels than the original form of AT-III. catalytic reactions using the iron(iv)-oxo porphyrin π-cation radical complex, [(tmp˙)Fe(O)], demonstrated that both H-atom abstraction and an oxygen rebound mechanism participated in the oxygenation process of AT-III.

CJ14939, a Novel JAK Inhibitor, Increases Oxaliplatin-induced Cell Death Through JAK/STAT Pathway in Colorectal Cancer.

Background/aim: Colorectal cancer is reported to have the highest mortality rate among human malignancies. Although many research results for the treatment of colorectal cancer have been reported, there is no suitable treatment when resistance has developed. Therefore, it is necessary to develop new therapeutic agents.

An end-on bis(μ-hydroxido) dimanganese(II,III) azide complex for C-H bond and O-H bond activation reactions.

We report the synthesis of an end-on dinuclear Mn(II) azide complex with two bridging azide ligands that served as a precursor for the formation of an end-on bis(μ-hydroxido) dinuclear Mn(II,III) azide complex upon oxidation by organic peroxide or peracids. Combined experimental and theoretical studies on the reactivity of the end-on bis(μ-hydroxido) dinuclear Mn(II,III) azide complex suggest that the reaction with substrates having weak C-H bond and O-H bond dissociation energy occurred a H-atom abstraction reaction in a concerted manner.

Mono- and dinuclear zinc complexes bearing identical bis(thiosemicarbazone) ligand that exhibit alkaline phosphatase-like catalytic reactivity.

Mono- and dinuclear zinc(II) complexes bearing bis(thiosemicarbazone) (bTSC) ligand were employed in the cleavage of phosphoester bonds. Comparative kinetic studies combined with theory suggested that the P-O bond cleavage is much accelerated by dinuclear zinc(II) complex in the presence of base. Based on the DFT-optimized structures of the proposed intermediates, it is plausible that (1) the removal of sulfur atoms of bTSC ligand from the zinc center provides two vacant sites for the binding of water (or hydroxide ion) and phosphoester and (2) the H-bonding between water (or hydroxide ion) and phosphoester, through several water molecules, may also assist the P-O bond cleavage and facilitate the nucleophilic attack.

Mutation SVCT2 promotes cell proliferation, invasion and migration in colorectal cancer.

The sodium-dependent vitamin C transporter 2 (SVCT2) surface glycoprotein regulates ascorbate accumulation in the plasma, often resulting in the induction of cancer cell death. Therefore, high expression of this gene associates with increased overall survival in several cancers. However, in colorectal cancer (CRC), high (likely mutated) expression relates to poor overall survival, and its functional significance has not been studied.

Synthesis, characterization and catalytic activity of a mononuclear nonheme copper(II)-iodosylbenzene adduct.

Iodosylbenzene (PhIO) and its derivatives have attracted significant attention due to their various applications in organic synthesis and biomimetic studies. For example, PhIO has been extensively used for generating high-valent metal-oxo species that have been regarded as key intermediates in diverse oxidative reactions in biological system. However, recent studies have shown that metal-iodosylbenzene adduct, known as a precursor of metal-oxo species, plays an important role in transition metal-catalyzed oxidation reactions.

Erlotinib Activates Different Cell Death Pathways in EGFR-mutant Lung Cancer Cells Grown in 3D 2D Culture Systems.

Background/aim: Non-small cell lung cancer patients with epidermal growth factor receptor (EGFR) mutation have been shown to have a good response to erlotinib, a receptor tyrosine kinase inhibitor of EGFR. In this study, we found that the cell death pathways activated by erlotinib in 2D and 3D culture systems are different.

Materials And Methods: The cell death pathways induced by erlotinib were evaluated by flow cytometry and immunoblotting in both 2D and 3D culture systems of EGFR mutant lung cancer cells.

Minimization of Torque Deviation of Cylinder Deactivation Engine through 48V Mild-Hybrid Starter-Generator Control.

Cylinder deactivation (CDA) is an effective technique to improve fuel economy in spark ignition (SI) engines. This technique enhances volumetric efficiency and reduces throttling loss. However, practical implementation is restricted due to torque fluctuations between individual cylinders that cause noise, vibration, and harshness (NVH) issues.