Fluorinated Macrocycle for Adsorptive Separation and Chromatographic Separation of Toluene and Methylcyclohexane.

Achieving the adsorptive separation and chromatographic separation of industrially the important chemicals toluene and methylcyclohexane using the same material is a highly desirable goal. We have successfully accomplished this using a fluorinated macrocycle tetrafluoroterphen[3]arene (4FTP3), which was synthesized and used for gas chromatographic separation in our previous work. The macrocycle 4FTP3 permitted the adsorptive separation of toluene from a toluene/methylcyclohexane mixture (1:1, v/v) with a purity of 99.

NEDD4-Mediated GSNOR Degradation Aggravates Cardiac Hypertrophy and Dysfunction.

Background: The decrease in S-nitrosoglutathione reductase (GSNOR) leads to an elevation of S-nitrosylation, thereby exacerbating the progression of cardiomyopathy in response to hemodynamic stress. However, the mechanisms under GSNOR decrease remain unclear. Here, we identify NEDD4 (neuronal precursor cell expressed developmentally downregulated 4) as a novel molecule that plays a crucial role in the pathogenesis of pressure overload-induced cardiac hypertrophy, by modulating GSNOR levels, thereby demonstrating significant therapeutic potential.

Allylic C-H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system.

Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C-H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji-Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C-H oxidation.

Homo-Mannich Reaction of Cyclopropanols: A Versatile Tool for Natural Product Synthesis.

ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to an imine or iminium ion, is one of the most widely used synthetic methods for the synthesis of β-amino carbonyl compounds. Nevertheless, the homo-Mannich reaction, which utilizes a homoenolate intermediate as the nucleophilic partner and provides straightforward access to the valuable γ-amino carbonyl compounds, remains underexplored. This can be largely attributed to the difficulties in generation and manipulation of the homoenolate species, despite various homoenolate equivalents that have been developed.

Palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles.

A novel palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles is described. A variety of new 3-carboxamide-3-allylation oxindoles with an all-carbon quaternary center were obtained in moderate to good yields (up to 99%). In addition, the asymmetric version of this reaction was also explored, providing moderate enantioselectivity.

Mimicking the Reactivity of LPMOs with a Mononuclear Cu Complex.

Lytic polysaccharide monooxygenases (LPMOs) are Cu-dependent metalloenzymes that catalyze the hydroxylation of strong C-H bonds in polysaccharides using O or HO as oxidants (monooxygenase/peroxygenase). In the absence of C-H substrate, LPMOs reduce O to HO (oxidase) and HO to HO (peroxidase) using proton/electron donors. This rich oxidative reactivity is promoted by a mononuclear Cu center in which some of the amino acid residues surrounding the metal might can accept and donate protons and/or electrons during O and HO reduction.

Synergistic Boronic Acid and Photoredox Catalysis: Synthesis of C-Branched Saccharides via Selective Alkylation of Unprotected Saccharides.

Here we present a regio- and stereoselective alkylation approach for unprotected saccharides using synergistic boronic acid and photoredox catalysis. Targeting the equatorial C-H bond of the -1,2-diol motif, this method employs MeB(OH) as a catalyst. Mechanistic investigations indicate that the formation of a tetracoordinate boron species, resulting from the interaction between the cyclic boronic diol ester and a free hydroxyl group in the saccharide, is critical to this transformation.

Rh(III)-Catalyzed Double Annulation of 3-Phenyl-1,2,4-oxadiazoles with 2-Diazo-1,3-diketones: Access to Pyran-Fused Isoquinolines.

Efficient access to pyranoisoquinoline derivatives via rhodium-catalyzed double C-H functionalization of phenyl oxadiazoles and diazo compounds has been developed. Two C-C bonds and one C-O and C-N bond formation was realized by this tandem reaction, along with the formation of two heterocycles, affording diversified pyran-fused isoquinolines in moderate to good yields with broad functional group tolerance under mild reaction conditions.

New Triterpenoids from the Leaves of and Their Anti-Inflammatory Activity.

Six new triterpenoids, heritieras C-H (-), along with thirteen known triterpenoids (-), were isolated from the leaves of . Their structures were identified by spectroscopic analysis, including 1D and 2D nuclear magnetic resonance (NMR), high-resolution electrospray ionization mass spectrometry (HRESIMS), and by comparison with the literature. Anti-inflammatory activity of the isolates was evaluated using the lipopolysaccharide (LPS) stimulated RAW 264.

Interaction Mechanisms of Cold Atmospheric Plasmas with HIV Capsid Protein by Reactive Molecular Dynamics Simulation.

In recent years, plasma medicine has developed rapidly as a new interdisciplinary discipline. However, the key mechanisms of interactions between cold atmospheric plasma (CAP) and biological tissue are still in the exploration stage. In this study, by introducing the reactive molecular dynamics (MD) simulation, the capsid protein (CA) molecule of HIV was selected as the model to investigate the reaction process upon impact by reactive oxygen species (ROS) from CAP and protein molecules at the atomic level.

Quantitative RNA pseudouridine maps reveal multilayered translation control through plant rRNA, tRNA and mRNA pseudouridylation.

Pseudouridine (Ψ) is the most abundant RNA modification, yet studies of Ψ have been hindered by a lack of robust methods to profile comprehensive Ψ maps. Here we utilize bisulfite-induced deletion sequencing to generate transcriptome-wide Ψ maps at single-base resolution across various plant species. Integrating ribosomal RNA, transfer RNA and messenger RNA Ψ stoichiometry with mRNA abundance and polysome profiling data, we uncover a multilayered regulation of translation efficiency through Ψ modifications.

Dynamic supramolecular snub cubes.

Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids and ferritin offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C-H hydrogen bonds.

Photoinduced Pd-Catalyzed 1,4-Dicarbofunctionalization of 1,3-Butadienes via Aliphatic C-H Bond Elaboration.

A three-component coupling strategy for 1,4-dicarbofunctionalization of 1,3-butadiene with C-H bearing substrates has been developed using photoinduced Pd catalysis, with aryl bromide serving as the hydrogen atom transfer (HAT) reagent. This photocatalytic coupling process achieves functionalized oxindole motifs in good yield and regioselectivity under mild reaction conditions. The versatility and synthetic utility of this method are demonstrated through the addition of a variety of C-H-bearing partners and various oxindole substrates to both substituted and unsubstituted butadiene.

Cobalt(II)-Catalyzed Selective C2-H Heck Reaction of Native (N-H) Indoles Enabled by Salicylaldehyde Ligand.

Direct functionalization of native (N-H) indoles via C-H activation remains a challenge. Herein, we report a salicylaldehyde-promoted cobalt-catalyzed selective C2-H Heck reaction of native (N-H) indoles with both active and unactivated olefins in the presence of free N-H bonds. A series of structurally diverse C2-alkenylated native (N-H) indoles including natural product and drug derivatives were prepared directly and effectively without additional preprotection and deprotection procedures.

GPR68 Mediates Lung Endothelial Dysfunction Caused by Bacterial Inflammation and Tissue Acidification.

Tissue acidification resulting from dysregulated cellular bioenergetics accompanies various inflammatory states. GPR68, along with other members of proton-sensing G protein-coupled receptors, responds to extracellular acidification and has been implicated in chronic inflammation-related diseases such as ischemia, cancer, and colitis. The present study examined the role of extracellular acidification on human pulmonary endothelial cell (EC) permeability and inflammatory status per se and investigated potential synergistic effects of acidosis on endothelial dysfunction caused by bacterial lipopolysaccharide (LPS, ).

Optimizing In Vivo Data Acquisition for Robust Clinical Microvascular Imaging Using Ultrasound Localization Microscopy.

Ultrasound localization microscopy (ULM) enables microvascular imaging at spatial resolutions beyond the acoustic diffraction limit, offering significant clinical potentials. However, ULM performance relies heavily on microbubble (MB) signal sparsity, the number of detected MBs, and signal-to-noise ratio (SNR), all of which vary in clinical scenarios involving bolus MB injections. These sources of variations underscore the need to optimize MB dosage, data acquisition timing, and imaging settings in order to standardize and optimize ULM of microvasculature.

Autogene cevumeran with or without atezolizumab in advanced solid tumors: a phase 1 trial.

Effective targeting of somatic cancer mutations to enhance the efficacy of cancer immunotherapy requires an individualized approach. Autogene cevumeran is a uridine messenger RNA lipoplex-based individualized neoantigen-specific immunotherapy designed from tumor-specific somatic mutation data obtained from tumor tissue of each individual patient to stimulate T cell responses against up to 20 neoantigens. This ongoing phase 1 study evaluated autogene cevumeran as monotherapy (n = 30) and in combination with atezolizumab (n = 183) in pretreated patients with advanced solid tumors.

Artificial Metalloenzymes with Two Catalytic Cofactors for Tandem Abiotic Transformations.

Artificial metalloenzymes (ArMs) enable the integration of abiotic cofactors within a native protein scaffold, allowing for non-natural catalytic activities. Previous ArMs, however, have primarily relied on single cofactor systems, limiting them to only one catalytic function. Here we present an approach to construct ArMs embedding two catalytic cofactors based on the biotin-streptavidin technology.

Aerobic oxidation of alkylarenes and polystyrene waste to benzoic acids a copper-based catalyst.

The chemical recycling of polystyrene (PS) waste to value-added aromatic compounds is an attractive but formidable challenge due to the inertness of the C-C bonds in the polymer backbone. Here we develop a light-driven, copper-catalyzed protocol to achieve aerobic oxidation of various alkylarenes or real-life PS waste to benzoic acid and oxidized styrene oligomers. The resulting oligomers can be further transformed under heating conditions, thus achieving benzoic acid in up to 65% total yield through an integrated one-pot two-step procedure.

Metal-Organic Frameworks with Phosphonate Monoester Linkers for Catalytic C(sp)-H Borylation of Alkenes.

An isoreticular metal-organic framework (MOF) series was constructed from nickel or cobalt nodes, phosphonate monoester, and bipyridine linkers. The cobalt-containing MOFs were found to catalyze the dehydrogenative C-H borylation of alkenes under mild conditions. This process selectively generates vinyl boronate without the formation of alkyl boronate byproducts and is insensitive to air, enabling large-scale preparation of the target products with isolated yields of over 80%.

Effect of Halogenation on the Optical, Electrical, and Thermal Properties of the Model Compound [Me(i-Pr)N][SnBr].

Organic-inorganic hybrid lead halides have been extensively studied due to their outstanding physical properties and diverse compositional elements. However, environmentally benign tin-based hybrids with remarkable flexibility in bandgap engineering have been less investigated. Herein, we report the successful design and synthesis of three tin-based organic-inorganic hybrid compounds through precise molecular modification: [Me(i-Pr)N][SnBr] (), [MeCHCl(i-Pr)N][SnBr] (), and [MeCHBr(i-Pr-Br)N][SnBr] ().

Targeting chromosomally unstable tumors with a selective KIF18A inhibitor.

Chromosome instability is a prevalent vulnerability of cancer cells that has yet to be fully exploited therapeutically. To identify genes uniquely essential to chromosomally unstable cells, we mined the Cancer Dependency Map for genes essential in tumor cells with high levels of copy number aberrations. We identify and validate KIF18A, a mitotic kinesin, as a vulnerability of chromosomally unstable cancer cells.

Pt/IrO enables selective electrochemical C-H chlorination at high current.

Employing electrochemistry for the selective functionalization of liquid alkanes allows for sustainable and efficient production of high-value chemicals. However, the large potentials required for C(sp)-H bond functionalization and low water solubility of such alkanes make it challenging. Here we discover that a Pt/IrO electrocatalyst with optimized Cl binding energy enables selective generation of Cl free radicals for C-H chlorination of alkanes.

Key Kinetic Interactions between NO and Unsaturated Hydrocarbons: H Atom Abstraction from C-C Alkynes, Dienes, and Trienes by NO.

An adequate understanding of the NO interacting chemistry is a prerequisite for a smoother transition to carbon-lean and carbon-free fuels such as ammonia and hydrogen. In this regard, this study presents a comprehensive study on the H atom abstraction by NO from C to C alkynes, dienes, and trienes forming 3 HNO isomers (i.e.