While photocatalytic CO reduction has been intensively investigated, reports on the influence of anions coordinated to catalytic metal sites on CO photoreduction remain limited. Herein, different coordinated anions (F, Cl, OAc, and NO ) around single Co sites installed on bipyridine-based three-component covalent organic frameworks (COFs) were synthesized, affording TBD-COF-Co-X (X = F, Cl, OAc, and NO), for photocatalytic CO reduction. Notably, the presence of these coordinated anions on the Co sites significantly influences the photocatalytic performance, where TBD-COF-Co-F exhibits superior activity to its counterparts.
View Article and Find Full Text PDFHerein, we demonstrate a practical dual ligand-enabled iron photocatalysis paradigm-converting all kinds of halogen-containing carboxylates (C X COO, X: F, Cl, Br) into C X radicals for the valuable chloro/fluoro-polyhaloalkylation of non-activated alkenes with easily available trichloroacetonitrile/Selectfluor as the electrophilic halogenation reagent. The modular assembly of the effective iron and C X COO-based light-harvesting species using the two ligands-OMe/CF-substituted bipyridine and acetonitrile/trichloroacetonitrile is evidenced by detailed mechanistic studies. The late-stage modification, low loading amount of iron (TON: 257) and feasible gram-scale synthesis show the utility of this protocol.
View Article and Find Full Text PDFPurpose: To evaluate the surveillance value of circulating tumor DNA (ctDNA) for detecting distant metastasis and indicating systemic therapeutic efficacy in conjunctival melanoma (CoM).
Design: Retrospective, observational case series.
Methods: From July 2021 to June 2023, 30 CoM patients in our center underwent plasma ctDNA assessment, out of which 12 individuals presented with distant metastases.
Janus TiPX (X = F, Cl, and Br) monolayers were systematically investigated through first-principles calculations. The Janus TiPX monolayers exhibit mechanical and dynamic stability. Two monolayers are indirect bandgap semiconductors, except the TiPBr monolayer, which has the features of a quasi-direct bandgap semiconductor.
View Article and Find Full Text PDFReforming sustainable 3d-metal-based visible light catalytic platforms for inert bulk chemical activation is highly desirable. Herein, we demonstrate the use of a Brønsted acid to unlock robust and practical iron ligand-to-metal charge transfer (LMCT) photocatalysis for the activation of multifarious inert haloalkylcarboxylates (CXCOO, X = F or Cl) to produce CX radicals. This process enables the fluoro-polyhaloalkylation of non-activated alkenes by combining easily available Selectfluor as a fluorine source.
View Article and Find Full Text PDFHistone deacetylase (HDAC) serves as a critical molecular regulator in the pathobiology of various malignancies and have garnered attention as a viable target for therapeutic intervention. A variety of HDAC inhibitors (HDACis) have been developed to target HDACs. Many preclinical studies have conclusively demonstrated the antitumor effects of HDACis, whether used as monotherapy or in combination treatments.
View Article and Find Full Text PDFEngineering F-rich solid electrolyte interphase (SEI) layers is regarded as an effective strategy to enable the long-term cycling stability of potassium-ion batteries (KIBs). However, in the conventional KPF carbonate electrolytes, it is challenging to form F-containing SEI layers due to the inability of KPF to decompose into KF. Herein, AlCl is employed as a novel additive to change the chemical environment of the KPF carbonate electrolyte.
View Article and Find Full Text PDFBackground And Objectives: Remote ischemic conditioning (RIC) is a low-cost, accessible, and noninvasive neuroprotective treatment strategy, but its efficacy and safety in acute ischemic stroke are controversial. With the publication of several randomized controlled trials (RCTs) and the recent results of the RESIST trial, it may be possible to identify the patient population that may (or may not) benefit from RIC. This systematic review and meta-analysis aims to evaluate the effectiveness and safety of RIC in patients with ischemic stroke receiving different treatments by pooling data of all randomized controlled studies to date.
View Article and Find Full Text PDFBackground: Angiogenesis, which plays a critical role in embryonic development and tissue repair, is controlled by a set of angiogenic signaling pathways. As a TF (transcription factor) belonging to the basic helix-loop-helix family, HEY (hairy/enhancer of split related with YRPW motif)-1 (YRPW motif, abbreviation of 4 highly conserved amino acids in the motif) has been identified as a key player in developmental angiogenesis. However, the precise mechanisms underlying HEY1's actions in angiogenesis remain largely unknown.
View Article and Find Full Text PDFThe magneto-optical Kerr effect (MOKE) is a powerful probe of magnetism and has recently gained new attention in antiferromagnetic (AFM) materials. Through extensive first-principles calculations and group theory analysis, we have identified FeCX (X = F, Cl) and Janus FeCFCl monolayers as ideal A-type collinear AFM materials with high magnetic anisotropy and Néel temperatures. By applying a vertical external electrical field () of 0.
View Article and Find Full Text PDFDielectric materials play an important role in devices for energy conversion and storage. Based on first-principles calculations, novel two-dimensional Janus GaOClX (X = F, Br, and I) monolayers with superior energy storage properties are predicted. They are indirect-bandgap semiconductors with bandgaps in the range of 2.
View Article and Find Full Text PDFFlexible solar cells have a lot of market potential for application in photovoltaics integrated into buildings and wearable electronics because they are lightweight, shockproof and self-powered. Silicon solar cells have been successfully used in large power plants. However, despite the efforts made for more than 50 years, there has been no notable progress in the development of flexible silicon solar cells because of their rigidity.
View Article and Find Full Text PDFHerein, hypervalent iodine-catalyzed halogenation of aryl-activated alkenes using BX (X = Cl, Br) as the halogen source and activating reagents was reported. Various halogenated 1,3-oxazine/2-oxazoline derivatives were obtained in good-to-high yields. Using BF resulted in different substitute sites from BBr and BCl of the products, indicating different reactive intermediates and reaction pathways.
View Article and Find Full Text PDFThe performance of iron-rich calcium sulfoaluminate (IR-CSA) cement is greatly affected by mineral composition and mineral activity in the clinker. This study aims to identify the effect of CaO sources, either CaCO or CaSO, on the phase formation and mineral composition of the IR-CSA clinker. Targeted samples were prepared with different proportions of CaCO and CaSO as CaO sources at 1300 °C for 45 min.
View Article and Find Full Text PDFMetallic Na is a promising metal anode for large-scale energy storage. Nevertheless, unstable solid electrolyte interphase (SEI) and uncontrollable Na dendrite growth lead to disastrous short circuit and poor cycle life. Through phase field and ab initio molecular dynamics simulation, we first predict that the sodium bromide (NaBr) with the lowest Na ion diffusion energy barrier among sodium halogen compounds (NaX, X=F, Cl, Br, I) is the ideal SEI composition to induce the spherical Na deposition for suppressing dendrite growth.
View Article and Find Full Text PDFBackground Although deep learning has brought revolutionary changes in health care, reliance on manually selected cross-sectional images and segmentation remain methodological barriers. Purpose To develop and validate an automated preoperative artificial intelligence (AI) algorithm for tumor and lymph node (LN) segmentation with CT imaging for prediction of LN metastasis in patients with pancreatic ductal adenocarcinoma (PDAC). Materials and Methods In this retrospective study, patients with surgically resected, pathologically confirmed PDAC underwent multidetector CT from January 2015 to April 2020.
View Article and Find Full Text PDFIntroduction: High risk of lymph node metastasis (LNM) in gastric papillary adenocarcinoma causes endoscopists to worry about the suitability of endoscopic resection for early gastric papillary adenocarcinoma (EPAC). We compared risk factors and attempted to establish a scoring system to stratify LNM risk in patients with EPAC.
Methods: A retrospective analysis was performed on 2,513 patients with early gastric carcinoma (EGC) who underwent radical resection in 4 tertiary hospitals in China.
Cr-Activated broadband near-infrared (NIR) luminescence materials are attracting much attention as next-generation smart NIR light sources that are widely used in night vision, bioimaging, medical treatment, and many other fields. Herein, a series of NaGaAlF:Cr NIR phosphors with broadband emission and tunable luminescence properties were designed and prepared. The luminescence intensity, peak position and full width at half maximum (FWHM) of the materials can be controlled by adjusting the crystal field strength.
View Article and Find Full Text PDFUltrathin two-dimensional metal-organic framework nanosheets have emerged as a promising kind of heterogeneous catalysts. Herein, we report a series of 2D porphyrinic metal-organic framework nanosheets (X-PMOF, X=F, Cl, Br), which was prepared from the self-assembly of a halogen-based porphyrin ligand X-TCPP (X-TCPP=5-(4-halogenatedphenyl)-10,15,20-tris(4-carboxyphenyl)-porphyrin) and ZrCl in the presence of trifluoroacetic acid as the modulating reagent. The framework of X-PMOF possessed the ftw topology as in MOF-525.
View Article and Find Full Text PDFWe present a strategy of self-nanocavity confinement for substantially boosting the superior electrochemical hydrogen peroxide (HO) selectivity for conductive metal-organic framework (MOF) materials. By using synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses, the dissociation of key *OOH intermediates during the oxygen reduction reaction (ORR) is effectively suppressed over the self-nanocavity-confined X-Ni MOF (X = F, Cl, Br, or I) catalysts, contributing to a favorable two-electron ORR pathway for highly efficient HO production. As a result, the as-prepared Br-confined Ni MOF catalyst significantly promotes HO selectivity up to 90% in an alkaline solution, evidently outperforming the pristine Ni MOF catalyst (40%).
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