Synthesis and diverse crystal packing in o-, m- and p-bis(carbonylthioureido)benzenes containing bisferrocenes.

Three bisferrocene-based bis(acylthiourea) positional isomers, namely, 1,2-bis(ferrocenylcarbonylthioureido)benzene (1), 1,3-bis(ferrocenylcarbonylthioureido)benzene (2) and 1,4-bis(ferrocenylcarbonylthioureido)benzene (3), all [Fe(CH)(CHNOS)], have been synthesized via facile nucleophilic addition reactions of 2.3 equivalents of ferrocenoyl isothiocyanate with o-, m- and p-phenylenediamine, respectively. The structures of the three new synthesized isomers were fully characterized by H NMR, C NMR, IR and UV-Vis spectroscopy, elemental analyses and cyclic voltammetry.

Selective Arene Photonitration via Iron-Complex β-Homolysis.

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields of pharmaceuticals, dyes, pesticides, functional materials, fertilizers, and explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge of fumes and waste acids, poor functional group tolerance, and tremendous purification difficulty, renders mild, efficient, and environmentally friendly nitration a formidable challenge. Herein, we develop a visible-light-driven biocompatible arene C-H nitration strategy with good efficiency and regioselectivity, marvelous substrate applicability and functional group tolerance, and wide application in scale-up synthesis, total synthesis, and late-stage functionalization.

Determining the Optimal Age for Extracranial-Intracranial Bypass Surgery: A Post Hoc Analysis of the CMOSS Randomized Trial.

Background: Previous trials have failed to demonstrate the benefits of extracranial-intracranial (EC-IC) bypass surgery for patients with carotid or middle cerebral artery occlusion. However, little evidence has focused on the effect of age on prognosis. This study aimed to explore whether EC-IC bypass surgery can provide greater benefits than medical therapy alone in specific age groups.

Triarylmethanol Derivatives with Ultralong Organic Room-Temperature Phosphorescence.

Triphenylmethyl-based compounds such as rhodamines and fluoresceine representing an old and well-known class of triphenylmethane dyes, are widely used in fluorescent labeling of bioimaging. Inspired by ultralong room temperature phosphorescence of triphenylphosphine derivatives, herein we report a methoxy substituted triarylmethanol ((4-methoxyphenyl)diphenylmethanol, LJW-1) exhibits ultralong room temperature phosphorescence (RTP) under ambient condition with afterglows of about 7 seconds. Its multiple C-H ⋅ ⋅ ⋅ π intermolecular interactions, C-H ⋅ ⋅ ⋅ O intermolecular interactions, hydrogen bond and π-π interactions are beneficial for forming rigid environment in the aggregated state which is evidently an important factor in the appearance of excellent RTP.

Copper(II)-Catalyzed Regioselective H/D Exchange Based on Reversible C-H Activation.

Despite the increasing use of copper in C-H functionalizations, the Cu-catalyzed direct deuteration of C-H bonds remains a significant challenge due to its inherent low reactivity in inverse C-H bond reconstruction. In this paper, a novel strategy had been developed to reverse the copper-catalyzed concerted metalation-deprotonation process by inhibiting the unexpected disproportionation of Cu(II) to Cu(III). Picolinic acid was identified as a powerful ligand for facilitating this H/D exchange with DO as deuterium source, and its inhibition activity was supported by preliminary control experiments and DFT studies.

Modulating the Amine-CO Interaction Strength: Toward Efficient Carbon Capture.

This study contributes to a comprehensive understanding of the interactions between CO and amines at the molecular level by exploring the rotational spectra of binary complexes between CO and eight different amines through pulsed-jet Fourier transform microwave spectroscopy and quantum chemical calculations. The findings reveal a consistent pattern in which CO is bonded to the amino group, primarily through a C···N tetrel bond, while being supported by C-H···O/C hydrogen bonds. Notably, the binding energies increase from primary through tertiary amines and with increasing chain length of the alkyl groups.

Palladium-Catalyzed Denitrative α-Arylation of Heteroarenes with Nitroarenes via C-H and C-NO Bond Activations.

A general approach for the α-arylation of heteroarenes with nitroarenes via denitrative coupling is reported for the first time. Various heteroarenes, including derivatives of furan, benzofuran, pyrrole, indole, thiophene, and benzothiophene, can be arylated at the α-position in moderate to good yields. Mechanistic studies demonstrate that the reaction proceeds via a CMD pathway, with C-H bond activation as the rate-determining step.

A Photoenzymatic Pathway for Gram-Scale Synthesis of 25-Hydroxyvitamin D.

Vitamin D and its analogues play a crucial role in promoting the well-being of both humans and animals. However, the current synthesis of this vital class of nutrients heavily relies on chemical transformations, which suffer from low step- and atom-efficiency due to lengthy synthetic pathways. To enhance sustainability in the chemical industry, it is necessary to develop alternative synthetic processes.

A Porphyrin-Faced ZnL Cage for Selective Oxidation of C(sp)-H Bonds and Sulfides.

Catalytic oxidation of benzyl C-H bonds and sulfides from fuel oils stands as an attractive proposition in the quest for clean energy, yet their simultaneous oxidation with a singular, economically friendly catalyst is not well established. In this work, the combination of a cobalt(II) porphyrin ligand with 2-pyridinecarboxaldehyde and Zn yielded a ZnL cage (Co cube). The three-dimensional conjugated structure effectively enhances energy transfer efficiency, enabling the Co cube to show a good ability to activate oxygen under light conditions for photooxidation.

Clinical Course, Therapy, and Long-Term Outcomes of Children With Moyamoya Disease and Posterior Cerebral Artery Involvement.

Background And Objectives: Posterior cerebral artery involvement (PCAi) has been identified as an important factor related to poor prognosis in moyamoya disease (MMD). This study summarized the characteristics of children with MMD and PCAi, clarified the clinical course, identified prognostic predictors, and investigated the long-term effect of encephaloduroarteriosynangiosis for posterior circulation (EDAS-p).

Methods: We retrospectively reviewed all our pediatric MMD cases with follow-up angiograms from November 2003 to December 2016.

Bifunctional Chiral Electrocatalysts Enable Enantioselective α-Alkylation of Aldehydes.

Herein, we describe an innovative approach to the asymmetric electrochemical α-alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α-alkylation of aldehydes.

Modifying Proton Relay into Bioinspired Dye-Based Coordination Polymer for Photocatalytic Proton-Coupled Electron Transfer.

Proton-coupled electron transfer (PCET) imparts an energetic advantage over single electron transfer in activating inert substances. Natural PCET enzyme catalysis generally requires tripartite preorganization of proton relay, substrate-bound active center, and redox mediator, making the processes efficient and precluding side reactions. Inspired by this, a heterogeneous photocatalytic PCET system was established to achieve higher PCET driving forces by modifying proton relays into anthraquinone-based anionic coordination polymers.

Rectifying METTL4-Mediated N-Methyladenine Excess in Mitochondrial DNA Alleviates Heart Failure.

Background: Myocardial mitochondrial dysfunction underpins the pathogenesis of heart failure (HF), yet therapeutic options to restore myocardial mitochondrial function are scarce. Epigenetic modifications of mitochondrial DNA (mtDNA), such as methylation, play a pivotal role in modulating mitochondrial homeostasis. However, their involvement in HF remains unclear.

Silver Surface-Assisted Dehydrobrominative Cross-Coupling between Identical Aryl Bromides.

Cross-coupling reactions represent an indispensable tool in chemical synthesis. An intriguing challenge in this field is to achieve selective cross-coupling between two precursors with similar reactivity or, to the limit, the identical molecules. Here we report an unexpected dehydrobrominative cross-coupling between 1,3,5-tris(2-bromophenyl)benzene molecules on silver surfaces.

Neoadjuvant-adjuvant pertuzumab in HER2-positive early breast cancer: final analysis of the randomized phase III PEONY trial.

The randomized, multicenter, double-blind, placebo-controlled, phase III PEONY trial (NCT02586025) demonstrated significantly improved total pathologic complete response (primary endpoint) with dual HER2 blockade in HER2-positive early/locally advanced breast cancer, as previously reported. Here, we present the final, long-term efficacy (secondary endpoints: event-free survival, disease-free survival, overall survival) and safety analysis (62.9 months' median follow-up).

Modulating the Electronic States of Pt Nanoparticles on Reducible Metal-Organic Frameworks for Boosting the Oxidation of Volatile Organic Compounds.

The adsorption and activation of pollutant molecules and oxygen play a critical role in the oxidation reaction of volatile organic compounds (VOCs). In this study, superior adsorption and activation ability was achieved by modulating the interaction between Pt nanoparticles (NPs) and UiO-66 (U6) through the spatial position effect. Pt@U6 exhibits excellent activity in toluene, acetone, propane, and aldehyde oxidation reactions.

Construction of an Angular Tricyclic Benzofuran Skeleton Using the C-H Activation Strategy.

A protocol for the construction of an angular tricyclic benzofuran skeleton based on the C-H activation strategy has been established. Different phthalide lactones on this skeleton can be easily assembled with various side chains by using C-H activation with aldehydes and subsequent reduction. This skeleton provides a versatile and crucial motif for the total synthesis of naturally occurring angular tricyclic benzofurans and their derivatives.

Reaction engineering blocks ether cleavage for synthesizing chiral cyclic hemiacetals catalyzed by unspecific peroxygenase.

Hemiacetal compounds are valuable building blocks in synthetic chemistry, but their enzymatic synthesis is limited and often hindered by the instability of hemiacetals in aqueous environments. Here, we show that this challenge can be addressed through reaction engineering by using immobilized peroxygenase from Agrocybe aegerita (AaeUPO) under neat reaction conditions, which allows for the selective C-H bond oxyfunctionalization of environmentally significant cyclic ethers to cyclic hemiacetals. A wide range of chiral cyclic hemiacetal products are prepared in >99% enantiomeric excess and 95170 turnover numbers of AaeUPO.

Synergistic Effects of In-Situ Exsolved Ni-Ru Bimetallic Catalyst on High-Performance and Durable Direct-Methane Solid Oxide Fuel Cells.

Direct-methane solid oxide fuel cells (CH-SOFCs) have gained significant attention as methane, the primary component of natural gas (NG), is cheap and widely available and the natural gas infrastructures are relatively mature. However, at intermediate temperatures (e.g.

Robotic-assisted navigation system for preoperative lung nodule localization: a pilot study.

Background: Preoperative percutaneous computed tomography (CT)-guided localization of pulmonary nodules plays a pivotal role in the diagnosis and treatment of early-stage lung cancer. However, conventional manual localization techniques have inherent limitations in achieving a high degree of accuracy. Consequently, a novel robotic-assisted navigation system was developed to attain precise localization of small lung nodules.

Photocatalytic C(sp)-H bond functionalization by Cu(I) halide cluster-mediated O activation.

Photocatalytic C-H bond activation is a challenging approach to selectively functionalize C(sp)-H bonds with dioxygen under mild conditions. Herein, by merging transition metal- and photo-catalysis, photoactive Cu(I)-halide(X) (X = Cl, Br, I) clusters are employed to effectively catalyse the selective monooxygenation and C-C oxidative cross-coupling of C(sp)-H bonds with unreactive O upon light irradiation. This modern protocol promises a photoinduced SET process between Cu(I)-clusters and O, and possibly forms Cu(II)-O˙ species for abstracting the H-atom from the C(sp)-H bond.