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.

Methacrylated poly(glycerol sebacate) as a photocurable, biocompatible, and biodegradable polymer with tunable degradation and drug release kinetics.

Poly(glycerol sebacate) (PGS) is a biodegradable, elastomeric polymer that has been explored for applications including tissue engineering, drug delivery, and wound repair. Despite its promise, its biomedical utility is limited by its rapid, and largely fixed, degradation rate. Additionally, its preparation requires prolonged curing at high temperatures, rendering it incompatible with heat-sensitive molecules, complex device geometries, and high-throughput production.

Mesoscale functional architecture in medial posterior parietal cortex.

The posterior parietal cortex () in mice has various functions including multisensory integration, vision-guided behaviors, working memory, and posture control. However, an integrated understanding of these functions and their cortical localizations in and around the PPC and higher visual areas (), has not been completely elucidated. Here we simultaneously imaged the activity of thousands of neurons within a 3 × 3 mm field-of-view, including eight cortical areas around the PPC, during behavior with a two-photon mesoscope.

Burden of Antimicrobial Resistance in Adult Hospitalized Patients With Cancer: A Multicenter Analysis.

Background: Infections are a leading cause of death in patients with cancer, but the proportion and rate of antimicrobial resistance (AMR) in hospitalized patients with cancer are not well understood.

Methods: This retrospective, cross-sectional evaluation of AMR assessed hospitalized adult patients in 168 United States (US) healthcare facilities between April 2018 and December 2022. Nonduplicate, noncontaminant Gram-negative and Gram-positive bacteria recovered from various samples (blood, respiratory, urine, etc.

Rh(II)-Catalyzed Selective C(sp)-H/C(sp)-H Bonds Cascade Insertion to Construct [6-8-6] Benzo-Fused Scaffold.

The fused eight-membered carbocycles (EMCs) play vital roles in the medicinal and biological investigations of many natural products and marketed drugs. The traditional synthesis of [6-8-6] benzo-fused derivatives involves multistep reactions and low yields, making the development of a one-step synthesis method a more challenging work. Here, we present a novel strategy for one-step construction of [6-8-6] benzo-fused scaffold from propargyl diazoacetates substituted with benzyl-nitrogen heterocyclic ring via Rh(ll)-catalyzed carbene/alkyne metathesis (CAM) and selective C-H bond insertion.

CeCl-Catalyzed C-H Alkylation of -Sulfonyl Ketimines with Alkanes and Ether via Photoinduced Ligand-to-Metal Charge Transfer.

A cerium-catalyzed C-H alkylation of -sulfonyl ketimines with low-cost and readily available alkanes as alkyl sources was developed. This transformation proceeded through the synergy of photoinitiated ligand-to-metal charge transfer (LMCT) using a chlorine radical as an HAT reagent and air as a green oxidant. A series of alkylated -sulfonyl ketimines were synthesized with moderate to good yields in a highly atom-economic manner under chemical oxidant-free conditions.

Ru-Catalyzed Switchable Reactions of Acrylic Acids with Glyoxylate: Access to Functionalized γ-Butenolides.

We herein report a switchable coupling of acrylic acids with ethyl glyoxylate under ruthenium catalysis enabling the synthesis of diverse functionalized γ-butenolides. The carboxyl-directed vinylic C-H cleavage and dual nucleophilic addition to aldehyde are achieved to deliver hydroxymethylated butanolides under mild and oxidant-free conditions. Alternatively, a controlled and unprecedented tandem C-H cyclization/oxidative homocoupling reaction is realized by using silver salt as the oxidant to generate a range of dimeric butenolides bearing vicinal all-carbon quaternary centers.

Au-Catalyzed 5C Reaction of Type II Diene-Ynenes toward Dihydrosemibullvalenes: Reaction Development and Mechanistic Study.

We report an unexpected gold-catalyzed 5C reaction of type II diene-ynenes to synthesize dihydrosemibullvalenes, which are potential bioisosteres for drug discovery. This 5C reaction occurs through a sequence of elementary reactions of cyclopropanation/Cope rearrangement/carbon shift/cyclopropanation/C-H insertion (shortened here as the 5C reaction), supported by quantum chemistry calculations. Mechanistic studies have also been applied to answer why type-II diene-ynenes cannot access seven-membered carbocycles-embedded bridged molecules under the gold catalysis, finding that the chair-like Cope rearrangement transition state (not the traditional boat-like transition state) is the key to the change of regiochemistry.

Palladium-catalyzed annulation and intermolecular hydroamination involving norbornene derivatives: synthesis of indanones and -alkylamines.

A palladium-catalyzed divergent reaction of primary benzamides using norbornene (NBE) derivatives as a controlled switch is reported. When NBE is used as a mediator, indanones are synthesized with moderate to good yields a Catellani reaction that involves sequential -C-H alkylation and -C-N bond cleavage annulation of primary benzamides. Employing norbornadiene (NBD) instead of NBE enables the assembly of -alkylamines by an intermolecular hydroamination reaction.

Elucidating Confinement and Microenvironment of Ru Clusters Stably Confined in MFI Zeolite for Efficient Propane Oxidation.

Achieving active and stable heterogeneous catalysts by encapsulating noble metal species within zeolites is highly promising for high utilization and cost efficiency in thermal and environmental catalytic reactions. Ru, considered an economical noble metal alternative with comparable performance, faces great challenges within MFI-type microporous zeolites due to its high cohesive energy and mobility. Herein, an innovative strategy was explored that couples hydrothermal in situ ligand protection with stepwise calcination in a flowing atmosphere to embed ultrasmall Ru clusters anchored at K-healed silanol sites (≡Si-Ru-O-K complexes) within 10-membered ring sinusoidal channels of MFI.

Integrative proteomic analyses across common cardiac diseases yield mechanistic insights and enhanced prediction.

Cardiac diseases represent common highly morbid conditions for which molecular mechanisms remain incompletely understood. Here we report the analysis of 1,459 protein measurements in 44,313 UK Biobank participants to characterize the circulating proteome associated with incident coronary artery disease, heart failure, atrial fibrillation and aortic stenosis. Multivariable-adjusted Cox regression identified 820 protein-disease associations-including 441 proteins-at Bonferroni-adjusted P < 8.

Regio- and Chemo-selective C-H Arylation of 3-Bromothiophene: A Synthesis Shortcut to Versatile π-Conjugated Building Blocks for Optoelectronic Materials.

Unlike traditional multi-step synthetic approaches, we developed a single-step synthesis of versatile π-conjugated building blocks bearing post-functionalizable C-H and C-Br bonds. Direct C-H arylation of 3-bromothiophene with various iodo(hetero)aryls was successfully carried out with good regio- and chemo-selectivity. Under optimized reaction conditions, 20 new compounds were facilely prepared in yields up to 91 %.

Early and noninvasive prediction of response to neoadjuvant therapy for breast cancer via longitudinal ultrasound and MR deep learning: A multicentre study.

Rationale And Objectives: The early prediction of response to neoadjuvant chemotherapy (NAC) will aid in the development of personalized treatments for patients with breast cancer. This study investigated the value of longitudinal multimodal deep learning (DL) based on breast MR and ultrasound (US) in predicting pathological complete response (pCR) after NAC.

Materials And Methods: We retrospectively reviewed the pre-NAC and post-2nd-NAC MR and/or US images of 448 patients enrolled from three centers and extracted DL features from the largest section of the breast tumour using ResNet50.

Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts.

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy for the activation of aryl thianthrenium salts using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating the need for external donors. Utilizing this EnT approach, we achieve C-H deuteration of arenes under visible light with CDCl as a deuterium source to synthesize various deuterated aromatic compounds, including important natural products and pharmaceuticals.

Enantioselective Propargylic C(sp)-H Acyloxylation Enabled by Photoexcited Copper Catalysis.

Direct C-H bond functionalization is an efficient method for modifying organic molecules. However, achieving high enantioselectivity and regioselectivity in asymmetric C-H functionalization, particularly of C(sp)-H bonds, remains challenging. This study introduces an enantioselective propargylic C(sp)-H acyloxylation using photoexcited copper catalysis.

Total synthesis of (-)-cylindrocyclophane A facilitated by C-H functionalization.

(-)-Cylindrocyclophane A is a 22-membered C-symmetric [7.7]paracyclophane that bears bis-resorcinol functionality and six stereocenters. We report a synthetic strategy for (-)-cylindrocyclophane A that uses 10 C-H functionalization reactions, resulting in a streamlined route with high enantioselectivity and efficiency (17 steps).

Recent Progress in Situ Application of HO Produced via Catalytic Synthesis.

Industrial production of HO requires lots of energy and causes environmental pollution. Moreover, in subsequent applications, much economic loss could be produced during the transportation process of HO and its dilution process. Therefore, it is highly desirable for in situ application of HO.

Heteroatom-Terminated Acrylate-Based Polymer-Dispersed Liquid Crystal Composite Films with High Contrast Ratio and Low Driving Voltage.

A series of polymer-dispersed liquid crystal (PDLC) films were prepared by using acrylate monomers containing heteroatom-terminated groups. The microscopic morphology and electro-optical properties reveal that these monomers effectively reduce the switching voltage and improve the contrast ratio at the same time. The saturation voltage of the best sample was reduced by 47%, and the contrast ratio was improved by 74%.

Copper-Catalyzed γ-C(sp)-H Lactamization and Iminolactonization.

Despite extensive efforts to develop γ-lactamization reactions for pyrrolidinone synthesis using either cyclometallation, C-H insertion, or radical C-H abstraction strategies, γ-lactamization reactions of aliphatic amides using practical catalysts and common protecting groups remain extremely rare. Herein we report copper-catalyzed γ-C(sp)-H lactamization and iminolactonization of tosyl-protected aliphatic amides using inexpensive Selectfluor as the sole oxidant. A switchable selectivity of γ-lactams or γ-iminolactones can be obtained by using two different sets of reaction conditions.

Impact of Photon-counting Detector Computed Tomography on a Quantitative Interstitial Lung Disease Machine Learning Model.

Purpose: Compare the impact of photon-counting detector computed tomography (PCD-CT) to conventional CT on an interstitial lung disease (ILD) quantitative machine learning (QML) model.

Materials And Methods: A QML model analyzed 52 CT exams from patients who underwent same-day conventional and PCD-CT for suspected ILD. Lin's concordance correlation coefficient (CCC) assessed agreement between conventional and PCD-CT QML results.

Hydroxyl Radical Mediated Heterogeneous Photocatalytic Baeyer-Villiger Oxidation over Covalent Triazine/Heptazine-Based Frameworks.

The Baeyer-Villiger (B-V) oxidation of ketones to the corresponding lactones/esters is a classic and essential reaction in the chemical industry. However, this oxidation process has not yet been achieved in ambient conditions with the aid of oxygen and heterogeneous photocatalysts. In this study, we developed an organic photocatalytic system using covalent triazine/heptazine-based frameworks (CTF-TB/CHF-TB) to enable the B-V oxidation reaction under mild conditions through a cascade reaction pathway.

Heteromultimetallic Platform for Enhanced C-H Bond Activation: Aluminum-Incorporated Dicopper Complex Mimicking Cu-ZSM-5 Structure and Oxidative Reactivity.

Bimetallic complexes have sparked interest across various chemical disciplines, driving advancements in research. Recent advancements in this field have shed light on complex reactions in metalloenzymes and unveiled new chemical transformations. Two primary types of bimetallic platforms have emerged: (1) systems where both metals actively participate in reactivity, and (2) systems where one metal mediates the reaction while the other regulates reactivity.

Catalyst-Controlled Chemoselective γ-C(sp)-H Lactonization of Carboxylic Acid: Methyl versus Methylene.

Despite recent advances in ligand-enabled C(sp)-H functionalization of native substrates, controlling chemoselectivity in the presence of methyl and methylene C(sp)-H bonds remains a significant challenge. Herein, we report the first example of the Pd(II)-catalyzed chemoselective lactonization of γ-methyl and methylene C(sp)-H bonds of carboxylic acids. Exclusive chemoselectivity of methyl or methylene γ-lactonization was achieved by using two different classes of Quinoline-Pyridone ligands.